WO2022156287A1 - Sulfo group-containing biochar flame-retardant wood-plastic board, and production method thereof - Google Patents
Sulfo group-containing biochar flame-retardant wood-plastic board, and production method thereof Download PDFInfo
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- WO2022156287A1 WO2022156287A1 PCT/CN2021/125580 CN2021125580W WO2022156287A1 WO 2022156287 A1 WO2022156287 A1 WO 2022156287A1 CN 2021125580 W CN2021125580 W CN 2021125580W WO 2022156287 A1 WO2022156287 A1 WO 2022156287A1
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/24—Structural elements or technologies for improving thermal insulation
- Y02A30/244—Structural elements or technologies for improving thermal insulation using natural or recycled building materials, e.g. straw, wool, clay or used tires
Definitions
- the present disclosure relates to the technical field of wood-plastic panels, in particular to a sulfonic acid-based biochar fire-retardant wood-plastic panel and a production method thereof.
- Wood-plastic composite is a new type of green material which is composed of wood fiber or plant fiber and thermoplastic polymer or other materials. It has excellent anti-corrosion performance, waterproof performance, thermal insulation performance and easy processing performance. Different from traditional wood-based panels, WPC production process has no waste gas, waste water discharge, no free formaldehyde and other harmful gases are released during use, can be recycled, and the raw materials are cheap, which can greatly ease the supply of wood resources in my country.
- the existing wood-plastic composite materials have a short service life and low high temperature resistance, so it is difficult to achieve the effect of flame retardant when used in wood-plastic panels. Not only that, because ordinary wood-plastic panels will be released quickly when burning. More smoke, which leads to a large amount of smoke and poisonous gas in the fire, becomes the main cause of casualties and hindering fire rescue.
- the purpose of the present disclosure is to provide a sulfonic acid-based biochar flame-retardant wood-plastic board and a production method thereof, so as to improve the flame-retardant effect of the wood-plastic board, and reduce the release speed and release amount of smoke during combustion.
- a sulfonic acid-based biochar fire-retardant wood-plastic board comprising the following components in parts by weight: 20-30 parts of bamboo and wood fiber powder, 90 parts of heavy calcium carbonate -110 parts, polyvinyl chloride resin powder 70-90 parts, PBS resin 9-15 parts, hollow ceramic microbeads 8-12 parts, ethylene-vinyl acetate copolymer 8-12 parts, sulfonated carbon 5.5-7.5 parts, heat 4-5 parts of stabilizer, 5-6 parts of foaming regulator, 0.6-1.2 part of foaming agent, 0.5-1 part of stearic acid, and 0.5-1 part of PE wax.
- the bamboo and wood fiber powder is processed into a dry state.
- the present disclosure also provides a method for producing the above-mentioned sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following steps:
- step (2) adding the mixed product obtained in step (1) into a screw extruder for extrusion molding.
- step (3) The material extruded in step (2) is shaped and cooled to room temperature.
- step (3) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
- the processing temperature in the screw extruder of step (2) is 170-180°C.
- sulfonated carbon as a solid acid catalyst, can catalyze wood or polymer to rapidly form carbon in advance when encountering high temperature, form a dense carbon layer barrier, can efficiently isolate heat and oxygen, and protect the underlying substrate, So as to play the role of fire retardant.
- the sulfonated carbon and the heavy calcium and resin in the wood-plastic board constitute a new type of intumescent flame-retardant system with "acid source, gas source, and carbon source” synergistically high-efficiency flame retardant.
- Sulfonated carbon/wood-plastic board The excellent flame retardant and smoke suppression performance of the system is due to the chemical reaction of the components interacting during the thermal decomposition process.
- the sulfonated carbon can not only promote the decomposition of CaCO 3 to release the gases CO 2 and H 2 O, but also rapidly promote the ethylene-vinyl acetate resin.
- PBS resin is cracked to produce a product whose end group is carboxylic acid, which can react with Ca 2+ to form an ionic polymer.
- the process of forming Ca ionic polymer leads to melt crosslinking, and crosslinking leads to an increase in melt viscosity, thereby It is beneficial to stabilize the expanded porous unstable carbon layer formed in the early stage of thermal decomposition, while the sulfonic acid abstracts chlorine from PVC to generate carbocations, and the carbocations are cross-linked through the Friedel-Crafts reaction to reduce volatile hydrocarbons.
- the formation of stable carbon on the surface of PVC is beneficial to stabilize the expanded porous unstable carbon layer formed in the early stage of thermal decomposition, while the sulfonic acid abstracts chlorine from PVC to generate carbocations, and the carbocations are cross-linked through the Friedel-Crafts reaction to reduce volatile hydrocarbons.
- the formation of stable carbon on the surface of PVC is beneficial to stabilize the expanded porous unstable carbon layer formed in the early stage of thermal decomposition, while the sulfonic acid abstracts chlorine from PVC to generate carbocations, and the carbocations are cross-linked through the Friedel
- the sulfonated carbon promotes the rapid carbonization of the polymer system, reduces the polymer fragments that can be combusted in the gas phase, and also reduces the heat on the surface of the polymer; the carbon layer with low thermal conductivity can make the incident polymer surface The energy is reflected out, thus protecting the underlying material, delaying the decomposition of the high polymer and the volatilization of the decomposition products.
- the physical structure of the thick foam carbon layer has good flame retardant performance. In order to suppress, it can effectively reduce the release speed and release amount of flue gas during combustion.
- Fig. 1 is the influence rule of sulfonated carbon addition on the oxygen index of bamboo and wood fiber integrated boards in the embodiment of the present disclosure
- Fig. 2 is the thermogravimetric curve diagram of the bamboo-wood fiber integrated board of different addition amounts of sulfonated carbon in the embodiment under nitrogen atmosphere;
- Fig. 3 is the heat release rate curve diagram of different bamboo and wood fiber integrated boards in the embodiment
- Fig. 4 is the total heat release curve diagram of different bamboo and wood fiber integrated boards in the embodiment
- Fig. 5 is the total smoke emission curve diagram of different bamboo and wood fiber integrated boards in the embodiment
- a sulfonic acid-based biochar fire-retardant wood-plastic board comprising the following components in parts by weight: 20 parts of bamboo and wood fiber powder processed into a dry state, 90 parts of heavy calcium carbonate, and 70 parts of polyvinyl chloride resin powder, 9 parts of PBS resin, 8 parts of hollow ceramic beads, 8 parts of ethylene-vinyl acetate copolymer, 5.5 parts of sulfonated carbon, 4 parts of heat stabilizer, 5 parts of foaming regulator, 0.6 parts of foaming agent, 0.5 parts of stearic acid parts, PE wax 0.5 parts.
- the co-extrusion of the base means that the main board (powder material) and the side board (granular material) are extruded at the same time.
- the co-extrusion mode can shorten the production cycle, and the extruded product has good integrity, high strength, easy to hold nails, and Make install.
- step (2) The material extruded in step (2) is shaped and cooled to room temperature, wherein, vacuum suction, water circulation cooling, traction and stretching can be adopted, and the cooling water in the shaping process can be recovered and reused.
- step (3) (4) cutting the material after shaping and cooling in step (3), and then carrying out matte filming treatment to obtain sulfonic acid-based biochar fire-retardant wood-plastic board.
- the whole process not only reduces energy consumption, but also saves human resources.
- the produced sheet has low formaldehyde emission and excellent mechanical properties.
- a sulfonic acid-based biochar fire-retardant wood-plastic board comprising the following components in parts by weight: 30 parts of bamboo and wood fiber powder processed into a dry state, 110 parts of heavy calcium carbonate, and 90 parts of polyvinyl chloride resin powder, 15 parts of PBS resin, 12 parts of hollow ceramic beads, 12 parts of ethylene-vinyl acetate copolymer, 7.5 parts of sulfonated carbon, 5 parts of heat stabilizer, 6 parts of foaming regulator, 1.2 parts of foaming agent, 1 part of stearic acid parts, PE wax 1 part.
- step (2) adding the mixed product obtained in step (1) into a screw extruder for extrusion molding, wherein the processing temperature in the screw extruder is 180°C.
- step (3) The material extruded in step (2) is shaped and cooled to room temperature.
- step (3) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
- a sulfonic acid-based biochar fire-retardant wood-plastic board comprising the following components in parts by weight: 25 parts of bamboo and wood fiber powder processed into a dry state, 100 parts of heavy calcium carbonate, 80 parts of polyvinyl chloride resin powder, 12 parts of PBS resin, 10 parts of hollow ceramic beads, 10 parts of ethylene-vinyl acetate copolymer, 6.5 parts of sulfonated carbon, 4.5 parts of heat stabilizer, 5.5 parts of foaming regulator, 0.9 parts of foaming agent, 0.8 parts of stearic acid parts, PE wax 0.8 parts.
- step (2) The mixed product obtained in step (1) was added to a screw extruder for extrusion molding, wherein the processing temperature in the screw extruder was 174°C.
- step (3) The material extruded in step (2) is shaped and cooled to room temperature.
- step (3) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
- the mechanism of flame retardant and smoke suppression of the sulfonic acid-based biochar flame retardant wood-plastic board in the above embodiments lies in the chemical reaction of the interaction of components during the thermal decomposition process.
- the addition of sulfonated carbon can not only promote the CaCO
- the decomposition releases CO 2 and H 2 O, and can rapidly promote the cracking of ethylene-vinyl acetate resin and PBS resin to produce a product whose end group is carboxylic acid, which reacts with Ca 2+ to form an ionic polymer.
- sulfonic acid abstracts chlorine from PVC to generate carbocations, and carbocations are cross-linked through Friedel-Crafts reaction, which reduces the generation of volatile hydrocarbons and forms stable carbon on the surface of PVC. Therefore, the sulfonated carbon promotes the rapid carbonization of the polymer system, reduces the polymer fragments that can be burned in the gas phase, and reduces the heat on the surface of the polymer; the carbon layer with low thermal conductivity can reflect the energy incident on the surface of the polymer. , thus protecting the underlying material, delaying the decomposition of the polymer and the volatilization of the decomposition products.
- the physical structure of the thick foam carbon layer has good flame retardant properties, heat release is reduced, and smoke is also suppressed.
- the sulfonated carbon is black particles, the shape is not significantly different from that before sulfonation, and the density and hardness are slightly increased. Due to the successful construction of sulfonic acid groups on the carbon skeleton, the adsorption performance is better than that of charcoal, and both perform in acid-catalyzed reactions. high catalytic activity and good stability.
- the sulfonic acid group can catalyze the dehydration of hydroxyl compounds into ester and carbon, and can also be thermally decomposed to generate SO 2 , CO 2 and H 2 O to inhibit the combustion of the substrate and reduce heat release; Reduce smoke and CO emissions. It can be seen that sulfonated carbon is an environmentally friendly flame retardant or flame retardant synergist.
- the selected wood-plastic board can be from one of the ones prepared in Examples 1-3, It can also be any combination of the components in the content of the invention in the weight ratio ratio range, which is not specifically limited here.
- the limiting oxygen index (LOI) test was carried out with reference to "Determination of Combustion Behavior by Oxygen Index Method for Plastics” (GB/T 2406.2-2009), and the sample size was 150mm ⁇ 5mm ⁇ 5mm.
- FIG. 1 shows the effect of sulfonated carbon addition on the oxygen index of bamboo and wood fiber integrated boards. It can be seen that the limiting oxygen index of the bamboo-wood fiber wood-plastic board without sulfonated carbon is 31.8, which is close to 32 of the B1 level. After adding 0.5% sulfonated carbon, the limiting oxygen index of bamboo-wood fiber integrated board is 32.7, which exceeds the B1 level requirement of GB50222-2017. With the increase of the addition of sulfonated carbon, the limit oxygen index of the bamboo-wood fiber composite board increases.
- the limit oxygen index is 36.1, and continues to increase to 3.0%, the limit oxygen index is 36.0, It shows that the effect of the continuous increase of sulfonated carbon on the limiting oxygen index is no longer significant, and the reasonable addition amount of sulfonated carbon is about 2.5%. This shows that 2.5% sulfonated carbon can better match the new intumescent flame retardant system composed of calcium carbonate, ethylene-vinyl acetate resin and PBS resin, which is conducive to better forming a thermal insulation and oxygen barrier carbon layer adhered to the base The surface of the material avoids the further spread of the flame and makes the flame self-extinguishing.
- the level combination of test 2 is A 1 B 2 C 2 D 2
- the level combination of test 3 is A 1 B 3 C 3 D 3
- the level combination of test 6 is A 2 B 3 C 1 D 2 .
- the single factor optimization of the extrusion molding conditions of the wood-plastic board was further carried out. From the data in Table 1-4, the influence of the extrusion temperature of the main board on the flexural strength of the wood-plastic board increases and then decreases with the increase of the temperature. Combining its influence on the limiting oxygen index, the optimal extrusion temperature is 174 °C.
- the extrusion temperature of the main plate ie the processing temperature in the screw extruder in the above embodiment
- the extrusion temperature of the main board was determined to be 174°C, and the extrusion pressure was determined to be 8.0 MPa. With the extension of time, the flexural strength and limiting oxygen index of the wood-plastic board increase, and it is more appropriate to choose the extrusion time of 60s (as shown in Table 1-6).
- thermogravimetric analyzer The thermal degradation performance of sulfonated carbon/bamboo wood fiber wood-plastic board was tested by TGA-Q500 thermogravimetric analyzer. Weigh 8-12 mg of dry powder and heat it from 40°C to 800°C at a heating rate of 10°C/min.
- the protective gas is high-purity nitrogen with a flow rate of 20 mL/min.
- thermogravimetric curves and data of bamboo-wood fiber integrated boards with different amounts of sulfonated carbon under nitrogen atmosphere are shown in Figure 2 and Table 2, respectively. It can be seen from the curve that the addition of sulfonated carbon did not significantly change the shape of the pyrolysis curve of the bamboo-wood fiber integrated board, but with the increase of sulfonated carbon, the degradation rate of the bamboo-wood fiber integrated board slowed down and the combustion residue increased, especially the 500 In the high temperature region above °C, the thermal stability of the residue increases significantly.
- T 5% of all samples degraded by 5% is not different, but the T 50% of the samples degraded by 50% is significantly different.
- T 50% is 734.2 °C, with With the increase of sulfonated carbon, T 50% increased, S-2.5% was 771.3°C, which was 37.1°C higher than S-0.0%.
- the British FTT cone calorimeter was used to measure the combustion performance of the sulfonated carbon/bamboo wood fiber wood-plastic board.
- the size of the test piece is 100mm ⁇ 100mm ⁇ 10mm (length ⁇ width ⁇ thickness).
- wrap all surfaces of the CONE sample of the cone calorimeter except the heated surface with aluminum foil put it in a stainless steel sample holder, block heat transfer at the bottom of the aluminum foil, and heat it at 50kW ⁇ m -2
- the surface temperature of the material was about 760°C when the samples were systematically studied and tested under irradiation power.
- the heat release rate HRR is the most important parameter to characterize the fire intensity, which refers to the heat release rate per unit area when the material burns under the preset radiation intensity.
- the combination of HRR and THR can objectively and comprehensively evaluate the combustion performance of materials.
- FIG. 3-1 The CONE experimental data of different bamboo and wood fiber integrated boards are listed in Table 3-1.
- Figures 3 and 4 are the heat release rate curves and total heat release curves of different bamboo and wood fiber integrated boards, respectively.
- the ignition time TTI time to ignition
- the flame extinction time FET flame extinction time
- the flame burning time is 287s; with the addition of sulfonated carbon, The ignition time of the samples increases, and the extinction time is advanced.
- the TTI of the samples S-2.0% and S-2.5% is the longest, which is 35s, the FET is the earliest, which is 190s, and the flame burning time is 155s, which is shorter than that of S-0.0%. 132s of open flame burning. From the heat release data of the CONE experiment, it can be seen that the addition of sulfonated carbon can effectively reduce the heat release.
- the peak PHRR of the highest heat release rate of S-2.5% is 16.7% lower than that of S-0.0%, which is 168.3kW/m 2 .
- the average heat release rate MHRR and the effective combustion EHC are 70.30kW/m 2 and 11.30MJ/kg, respectively.
- the 95.30kW/m 2 of S-0.0% is reduced by 25.00kW/m 2 and 2.79MJ/kg, respectively, which are 26.2% and 19.8% ; -0.0% THR38.13MJ/m 2 decreased by 49.5%.
- the Fire Spread Index (FGI) is the ratio of the peak heat release rate (PHRR) to the time to peak (t PHRR ).
- the FGI of S-0.0% is 4.04kw/sm 2 .
- the FGI of S-2.5% is 1.02kw/sm 2 , less than S-0.0 A quarter of %FGI. It shows that the addition of sulfonated carbon can effectively inhibit the heat release of bamboo and wood fiber wood-plastic panels, reduce the spread of flames, and reduce the risk of fire.
- Smoke and poisonous gas are the main causes of casualties in fires.
- Toxic gas causes people to suffocate, smoke reduces visibility in the fire scene, prevents firefighters from entering the fire scene for rescue, and makes it difficult for people at the fire scene to evacuate and escape.
- 70% to 80% of fire deaths are caused by smoke and toxic gas suffocation. Therefore, smoke and toxic gases are important factors that cause casualties in fires.
- the CONE smoke data of different bamboo and wood fiber integrated boards are shown in Table 3-2, and the total smoke emission curve is shown in Figure 5.
- SPR and TSP are further reduced, SPR of S-2.5% is reduced to 486.4m 2 /s, only 35.2% of S-0.0%; TSP is 4.99m 2 /m 2 , which is lower than that of S-0.0 % decreased by 7.3m 2 /m 2 , about 59.4%.
- CO is the most important factor causing suffocation and poisoning in fires.
- the addition of sulfonated carbon can effectively reduce the production of carbon monoxide. The addition of 2.5% reduces the production of carbon monoxide from 45.5g/kg to 21.4g/kg. 53.0%.
- the reduction of CO is mainly due to the catalytic carbonization of the bamboo-wood fiber system by the sulfonated carbon.
- the rapid carbonization rate and excellent carbonization quality make the samples under the carbon layer Being efficiently protected, the flame goes out faster and the burning time is shortened.
- the electron microscope photo of the bamboo-wood fiber integrated board is shown in Figure 6. It can be seen from the figure that the S-0.0% carbon residue without sulfonated carbon has many pores and different sizes, and the pores are deep, and the surface of the carbon residue is powdery and not connected. overall. After adding sulfonated carbon, the surface of the sample carbon residue changed obviously, the pores of S-0.5% decreased, but the individual pores were still deep; with the increase of sulfonated carbon, S-1.0%, S-1.5%, S-2.0 % and S-2.5% pores gradually decrease, and the uniformity of pores increases, and the integrity and compactness of the carbon layer are getting better and better.
- the sulfonic acid-based biochar flame-retardant wood-plastic board provided by the above embodiment complies with T/CADBM3-2018 "Bamboo and Wood Fiber Integrated Wallboard", GB18580-2017 "Formaldehyde Release in Wood-based Panels of Interior Decoration Materials and Their Products", "2020”
- the sulfonated carbon/bamboo wood fiber wood-plastic board (ie, sulfonic acid-based biochar flame-retardant wood-plastic board) product and its preparation process are green and environmentally friendly, and are ideal materials for people's green homes.
- Sulfonated carbon/bamboo fiber wood-plastic board products have good functionality and market application prospects. Its production technology can be completely upgraded in the traditional wood-plastic board production line. Compared with traditional wood-plastic boards, its products are environmentally friendly. , flame retardant, light weight and high strength and other functional advantages.
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Abstract
A sulfo group-containing biochar flame-retardant wood-plastic board, and a production method thereof, relating to the technical field of wood-plastic boards and comprising the following components in parts by weight: 20-30 parts of bamboo fiber powder, 90-110 parts of heavy calcium carbonate, 70-90 parts of polyvinyl chloride resin powder, 9-15 parts of PBS resin, 8-12 parts of hollow ceramic microbeads, 8-12 parts of ethylene-vinyl acetate copolymer, 5.5-7.5 parts of sulfonated carbon, 4-5 parts of a heat stabilizer, 5-6 parts of a foaming regulator, 0.6-1.2 parts of a foaming agent, 0.5-1 part of stearic acid and 0.5-1 part of PE wax. The present disclosure can improve the flame-retardant effect of the wood-plastic board and reduce the speed and amount of smoky gas released during combustion.
Description
本公开涉及木塑板技术领域,尤其指一种磺酸基生物炭阻燃木塑板及其生产方法。The present disclosure relates to the technical field of wood-plastic panels, in particular to a sulfonic acid-based biochar fire-retardant wood-plastic panel and a production method thereof.
随着经济的发展和社会的进步,人们生活质量的不断提高,木材及其他林产品的需求日益增加,而林产品的国际进口难度不断增加,所以木材供需矛盾有增无减。针对供需现状,国内外学者进行了深入的研究,解决木材供需矛盾的方法:一是充分高效利用现有的木材资源,提高木材利用率;二是寻找木材制品的替代产品,减少木材消耗。With economic development and social progress, people's quality of life continues to improve, the demand for timber and other forest products is increasing, and the difficulty of international import of forest products is increasing, so the contradiction between supply and demand of timber continues unabated. In response to the current situation of supply and demand, scholars at home and abroad have conducted in-depth research to solve the contradiction between wood supply and demand: one is to make full and efficient use of existing wood resources to improve the utilization rate of wood; the other is to find alternative products for wood products to reduce wood consumption.
木塑复合材料(WPC)是木纤维或植物纤维与热塑性聚合物或其他材料复合而成的新型绿色材料,具有优良的防腐性能、防水性能、热绝缘性能及易加工性能等。与传统的人造板不同,WPC生产过程无废气,废水排放,使用过程中无游离甲醛等有害气体释放,可循环使用,而且原料价格低廉,可以大大缓解我国木材资源的供应。Wood-plastic composite (WPC) is a new type of green material which is composed of wood fiber or plant fiber and thermoplastic polymer or other materials. It has excellent anti-corrosion performance, waterproof performance, thermal insulation performance and easy processing performance. Different from traditional wood-based panels, WPC production process has no waste gas, waste water discharge, no free formaldehyde and other harmful gases are released during use, can be recycled, and the raw materials are cheap, which can greatly ease the supply of wood resources in my country.
现有的木塑符合材料的使用寿命不长、耐高温性能也不是很理想,因此利用到木塑板中很难达到阻燃的效果,不仅如此,由于普通木塑板在燃烧时会快速释放较多的烟气,这导致火灾中会产生大量的烟雾与毒气,成为造成人员伤亡、妨碍消防救援的主要原因。The existing wood-plastic composite materials have a short service life and low high temperature resistance, so it is difficult to achieve the effect of flame retardant when used in wood-plastic panels. Not only that, because ordinary wood-plastic panels will be released quickly when burning. More smoke, which leads to a large amount of smoke and poisonous gas in the fire, becomes the main cause of casualties and hindering fire rescue.
发明内容SUMMARY OF THE INVENTION
本公开的目的在于提供一种磺酸基生物炭阻燃木塑板及其生产方法,提高木塑板的阻燃效果,并降低其燃烧时烟气的释放速度和释放量。The purpose of the present disclosure is to provide a sulfonic acid-based biochar flame-retardant wood-plastic board and a production method thereof, so as to improve the flame-retardant effect of the wood-plastic board, and reduce the release speed and release amount of smoke during combustion.
为了解决上述技术问题,本公开采用如下技术方案:一种磺酸基生物炭阻燃木塑板,包括以下重量份配比的组成成分:竹木纤维粉20-30份,重质碳酸钙90-110份,聚氯乙烯树脂粉70-90份,PBS树脂9-15份,空心陶瓷微珠8-12份,乙烯-醋酸乙烯共聚物8-12份,磺化炭5.5-7.5份,热稳定剂4-5份,发泡调节剂5-6份,发泡剂0.6-1.2份,硬脂酸0.5-1份,PE蜡0.5-1份。In order to solve the above-mentioned technical problems, the present disclosure adopts the following technical solutions: a sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following components in parts by weight: 20-30 parts of bamboo and wood fiber powder, 90 parts of heavy calcium carbonate -110 parts, polyvinyl chloride resin powder 70-90 parts, PBS resin 9-15 parts, hollow ceramic microbeads 8-12 parts, ethylene-vinyl acetate copolymer 8-12 parts, sulfonated carbon 5.5-7.5 parts, heat 4-5 parts of stabilizer, 5-6 parts of foaming regulator, 0.6-1.2 part of foaming agent, 0.5-1 part of stearic acid, and 0.5-1 part of PE wax.
优选地,所述竹木纤维粉为处理成干燥状态的竹木纤维粉。Preferably, the bamboo and wood fiber powder is processed into a dry state.
另外,本公开还提供一种生产上述磺酸基生物炭阻燃木塑板的方法,其包括 以下步骤:In addition, the present disclosure also provides a method for producing the above-mentioned sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following steps:
(1)将竹木纤维粉、重质碳酸钙、聚氯乙烯树脂粉、PBS树脂、空心陶瓷微珠、乙烯醋酸乙烯共聚物、磺化炭、热稳定剂、发泡调节剂、发泡剂、硬脂酸、PE蜡按照所述重量份配比混合搅拌均匀并塑化,得到混匀物。(1) Combine bamboo and wood fiber powder, heavy calcium carbonate, polyvinyl chloride resin powder, PBS resin, hollow ceramic microbeads, ethylene vinyl acetate copolymer, sulfonated carbon, heat stabilizer, foaming regulator, foaming agent , stearic acid and PE wax are mixed and stirred uniformly and plasticized according to the stated weight portion ratio to obtain a uniform mixture.
(2)将步骤(1)中得到的混匀物加入到螺杆挤出机中进行挤出成型。(2) adding the mixed product obtained in step (1) into a screw extruder for extrusion molding.
(3)使步骤(2)中挤出成型的物料定型并冷却至室温。(3) The material extruded in step (2) is shaped and cooled to room temperature.
(4)将步骤(3)中定型并冷却后的物料切割,然后进行亚光贴膜处理,从而制得磺酸基生物炭阻燃木塑板。(4) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
优选地,在步骤(2)的螺杆挤出机中的加工温度为170~180℃。Preferably, the processing temperature in the screw extruder of step (2) is 170-180°C.
本公开的有益效果在于:磺化炭作为固体酸催化剂,在遭遇高温时可催化木材或聚合物快速提前成炭,形成致密的炭层屏障,能高效地隔绝热、氧气,保护下层基材,从而起到阻燃防火的作用。The beneficial effects of the present disclosure are as follows: sulfonated carbon, as a solid acid catalyst, can catalyze wood or polymer to rapidly form carbon in advance when encountering high temperature, form a dense carbon layer barrier, can efficiently isolate heat and oxygen, and protect the underlying substrate, So as to play the role of fire retardant.
具体来说,磺化炭与木塑板中的重钙、树脂等构成了“酸源、气源、炭源”三源协同高效阻燃的新型膨胀阻燃体系,磺化炭/木塑板体系优异的阻燃抑烟性能是由于热分解过程中组分相互作用发生的化学反应,磺化炭不仅可促使CaCO
3分解释放气体CO
2和H
2O,且能快速促进乙烯-醋酸乙烯树脂、PBS树脂裂解,产生端基为羧酸的产物,该产物可与Ca
2+反应形成离子聚合物,形成Ca离子聚合物的过程导致融体交联,交联则导致融体黏度增加,从而有利于稳定热分解初期所形成的膨胀多孔的不稳定的炭层,同时磺酸从PVC中夺取氯生成碳正离子,而碳正离子通过Friedel-Crafts反应而发生交联,以减少挥发性烃的生成,在PVC表面形成稳定的炭。
Specifically, the sulfonated carbon and the heavy calcium and resin in the wood-plastic board constitute a new type of intumescent flame-retardant system with "acid source, gas source, and carbon source" synergistically high-efficiency flame retardant. Sulfonated carbon/wood-plastic board The excellent flame retardant and smoke suppression performance of the system is due to the chemical reaction of the components interacting during the thermal decomposition process. The sulfonated carbon can not only promote the decomposition of CaCO 3 to release the gases CO 2 and H 2 O, but also rapidly promote the ethylene-vinyl acetate resin. , PBS resin is cracked to produce a product whose end group is carboxylic acid, which can react with Ca 2+ to form an ionic polymer. The process of forming Ca ionic polymer leads to melt crosslinking, and crosslinking leads to an increase in melt viscosity, thereby It is beneficial to stabilize the expanded porous unstable carbon layer formed in the early stage of thermal decomposition, while the sulfonic acid abstracts chlorine from PVC to generate carbocations, and the carbocations are cross-linked through the Friedel-Crafts reaction to reduce volatile hydrocarbons. The formation of stable carbon on the surface of PVC.
所以,磺化炭促进聚合物体系快速成炭,减少可在气相中燃烧的高聚物碎片,同时也减少了高聚物表面的热量;导热量低的炭层能使入射高聚物表面的能量反射出去,因而保护了其下层材料,延缓了高聚物的分解及分解产物的挥发,厚实的泡沫炭层的物理结构具有良好的阻燃性能,在热释放减少的同时,烟气也得到了抑制,从而能够有效降低燃烧时烟气的释放速度和释放量。Therefore, the sulfonated carbon promotes the rapid carbonization of the polymer system, reduces the polymer fragments that can be combusted in the gas phase, and also reduces the heat on the surface of the polymer; the carbon layer with low thermal conductivity can make the incident polymer surface The energy is reflected out, thus protecting the underlying material, delaying the decomposition of the high polymer and the volatilization of the decomposition products. The physical structure of the thick foam carbon layer has good flame retardant performance. In order to suppress, it can effectively reduce the release speed and release amount of flue gas during combustion.
图1为本公开实施例中磺化炭添加量对竹木纤维集成板氧指数的影响规律;Fig. 1 is the influence rule of sulfonated carbon addition on the oxygen index of bamboo and wood fiber integrated boards in the embodiment of the present disclosure;
图2为实施例中不同添加量磺化炭的竹木纤维集成板在氮气氛围下的热失重曲线图;Fig. 2 is the thermogravimetric curve diagram of the bamboo-wood fiber integrated board of different addition amounts of sulfonated carbon in the embodiment under nitrogen atmosphere;
图3为实施例中不同竹木纤维集成板的热释放速率曲线图;Fig. 3 is the heat release rate curve diagram of different bamboo and wood fiber integrated boards in the embodiment;
图4为实施例中不同竹木纤维集成板的总热释放量曲线图;Fig. 4 is the total heat release curve diagram of different bamboo and wood fiber integrated boards in the embodiment;
图5为实施例中不同竹木纤维集成板的总烟释放量曲线图;Fig. 5 is the total smoke emission curve diagram of different bamboo and wood fiber integrated boards in the embodiment;
图6为实施例中木塑板燃烧后的Mag=100X规格电镜照片示意图;Fig. 6 is the Mag=100X specification electron microscope photograph schematic diagram after the wood-plastic board is burned in the embodiment;
图7为实施例中木塑板燃烧后的Mag=1.0KX规格电镜照片示意图。FIG. 7 is a schematic diagram of an electron microscope photograph of the Mag=1.0KX specification after the wood-plastic board is burned in the embodiment.
为了便于本领域技术人员的理解,下面结合实施例与附图对本公开作进一步的说明,实施方式提及的内容并非对本公开的限定。In order to facilitate the understanding of those skilled in the art, the present disclosure will be further described below with reference to the embodiments and the accompanying drawings, and the contents mentioned in the embodiments are not intended to limit the present disclosure.
实施例1Example 1
一种磺酸基生物炭阻燃木塑板,包括以下重量份配比的组成成分:处理成干燥状态的竹木纤维粉20份,重质碳酸钙90份,聚氯乙烯树脂粉70份,PBS树脂9份,空心陶瓷微珠8份,乙烯-醋酸乙烯共聚物8份,磺化炭5.5份,热稳定剂4份,发泡调节剂5份,发泡剂0.6份,硬脂酸0.5份,PE蜡0.5份。A sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following components in parts by weight: 20 parts of bamboo and wood fiber powder processed into a dry state, 90 parts of heavy calcium carbonate, and 70 parts of polyvinyl chloride resin powder, 9 parts of PBS resin, 8 parts of hollow ceramic beads, 8 parts of ethylene-vinyl acetate copolymer, 5.5 parts of sulfonated carbon, 4 parts of heat stabilizer, 5 parts of foaming regulator, 0.6 parts of foaming agent, 0.5 parts of stearic acid parts, PE wax 0.5 parts.
生产方法:production method:
(1)将竹木纤维粉、重质碳酸钙、聚氯乙烯树脂粉、PBS树脂、空心陶瓷微珠、乙烯醋酸乙烯共聚物、磺化炭、热稳定剂、发泡调节剂、发泡剂、硬脂酸、PE蜡按照上述重量份配比混合搅拌均匀并塑化,得到混匀物。其中,可采用大体积冷锅慢混的方式,一次可完成2吨原材料的均匀共混,比传统热锅共混可节约电能2000多千瓦/天。(1) Combine bamboo and wood fiber powder, heavy calcium carbonate, polyvinyl chloride resin powder, PBS resin, hollow ceramic microbeads, ethylene vinyl acetate copolymer, sulfonated carbon, heat stabilizer, foaming regulator, foaming agent , stearic acid and PE wax are mixed and stirred uniformly and plasticized according to the above-mentioned proportion by weight to obtain a uniform mixture. Among them, the method of slow mixing in a large volume of cold pot can be used to complete the uniform blending of 2 tons of raw materials at one time, which can save more than 2,000 kilowatts/day of electricity compared with traditional hot pot blending.
(2)将步骤(1)中得到的混匀物加入到螺杆挤出机中进行挤出成型,其中,螺杆挤出机中的加工温度为170℃,作为优选地,可采用一模头二基座的共挤,即一次完成主板(粉末料)、边板(颗粒料)的同时挤出成型,共挤模式能缩短制作周期,挤出产品整体性好、强度高、便于握钉,易于制作安装。(2) adding the mixture obtained in the step (1) into a screw extruder for extrusion molding, wherein the processing temperature in the screw extruder is 170 ° C, and preferably, one die and two The co-extrusion of the base means that the main board (powder material) and the side board (granular material) are extruded at the same time. The co-extrusion mode can shorten the production cycle, and the extruded product has good integrity, high strength, easy to hold nails, and Make install.
(3)使步骤(2)中挤出成型的物料定型并冷却至室温,其中,可采用真空吸气、水循环冷却、牵引拉伸定型,定型过程中的冷却水回收,重复循环使用。(3) The material extruded in step (2) is shaped and cooled to room temperature, wherein, vacuum suction, water circulation cooling, traction and stretching can be adopted, and the cooling water in the shaping process can be recovered and reused.
(4)将步骤(3)中定型并冷却后的物料切割,然后进行亚光贴膜处理,从 而制得磺酸基生物炭阻燃木塑板。整个工艺过程不仅降低能耗,还能节约人力资源,生产的板材甲醛释放量低,力学性能优良。(4) cutting the material after shaping and cooling in step (3), and then carrying out matte filming treatment to obtain sulfonic acid-based biochar fire-retardant wood-plastic board. The whole process not only reduces energy consumption, but also saves human resources. The produced sheet has low formaldehyde emission and excellent mechanical properties.
实施例2Example 2
一种磺酸基生物炭阻燃木塑板,包括以下重量份配比的组成成分:处理成干燥状态的竹木纤维粉30份,重质碳酸钙110份,聚氯乙烯树脂粉90份,PBS树脂15份,空心陶瓷微珠12份,乙烯-醋酸乙烯共聚物12份,磺化炭7.5份,热稳定剂5份,发泡调节剂6份,发泡剂1.2份,硬脂酸1份,PE蜡1份。A sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following components in parts by weight: 30 parts of bamboo and wood fiber powder processed into a dry state, 110 parts of heavy calcium carbonate, and 90 parts of polyvinyl chloride resin powder, 15 parts of PBS resin, 12 parts of hollow ceramic beads, 12 parts of ethylene-vinyl acetate copolymer, 7.5 parts of sulfonated carbon, 5 parts of heat stabilizer, 6 parts of foaming regulator, 1.2 parts of foaming agent, 1 part of stearic acid parts, PE wax 1 part.
生产方法:production method:
(1)将竹木纤维粉、重质碳酸钙、聚氯乙烯树脂粉、PBS树脂、空心陶瓷微珠、乙烯醋酸乙烯共聚物、磺化炭、热稳定剂、发泡调节剂、发泡剂、硬脂酸、PE蜡按照上述重量份配比混合搅拌均匀并塑化,得到混匀物。(1) Combine bamboo and wood fiber powder, heavy calcium carbonate, polyvinyl chloride resin powder, PBS resin, hollow ceramic microbeads, ethylene vinyl acetate copolymer, sulfonated carbon, heat stabilizer, foaming regulator, foaming agent , stearic acid and PE wax are mixed and stirred uniformly and plasticized according to the above-mentioned proportion by weight to obtain a uniform mixture.
(2)将步骤(1)中得到的混匀物加入到螺杆挤出机中进行挤出成型,其中,螺杆挤出机中的加工温度为180℃。(2) adding the mixed product obtained in step (1) into a screw extruder for extrusion molding, wherein the processing temperature in the screw extruder is 180°C.
(3)使步骤(2)中挤出成型的物料定型并冷却至室温。(3) The material extruded in step (2) is shaped and cooled to room temperature.
(4)将步骤(3)中定型并冷却后的物料切割,然后进行亚光贴膜处理,从而制得磺酸基生物炭阻燃木塑板。(4) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
实施例3Example 3
一种磺酸基生物炭阻燃木塑板,包括以下重量份配比的组成成分:处理成干燥状态的竹木纤维粉25份,重质碳酸钙100份,聚氯乙烯树脂粉80份,PBS树脂12份,空心陶瓷微珠10份,乙烯-醋酸乙烯共聚物10份,磺化炭6.5份,热稳定剂4.5份,发泡调节剂5.5份,发泡剂0.9份,硬脂酸0.8份,PE蜡0.8份。A sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following components in parts by weight: 25 parts of bamboo and wood fiber powder processed into a dry state, 100 parts of heavy calcium carbonate, 80 parts of polyvinyl chloride resin powder, 12 parts of PBS resin, 10 parts of hollow ceramic beads, 10 parts of ethylene-vinyl acetate copolymer, 6.5 parts of sulfonated carbon, 4.5 parts of heat stabilizer, 5.5 parts of foaming regulator, 0.9 parts of foaming agent, 0.8 parts of stearic acid parts, PE wax 0.8 parts.
生产方法:production method:
(1)将竹木纤维粉、重质碳酸钙、聚氯乙烯树脂粉、PBS树脂、空心陶瓷微珠、乙烯醋酸乙烯共聚物、磺化炭、热稳定剂、发泡调节剂、发泡剂、硬脂酸、PE蜡按照上述重量份配比混合搅拌均匀并塑化,得到混匀物。(1) Combine bamboo and wood fiber powder, heavy calcium carbonate, polyvinyl chloride resin powder, PBS resin, hollow ceramic microbeads, ethylene vinyl acetate copolymer, sulfonated carbon, heat stabilizer, foaming regulator, foaming agent , stearic acid and PE wax are mixed and stirred uniformly and plasticized according to the above-mentioned proportion by weight to obtain a uniform mixture.
(2)将步骤(1)中得到的混匀物加入到螺杆挤出机中进行挤出成型,其中,螺杆挤出机中的加工温度为174℃。(2) The mixed product obtained in step (1) was added to a screw extruder for extrusion molding, wherein the processing temperature in the screw extruder was 174°C.
(3)使步骤(2)中挤出成型的物料定型并冷却至室温。(3) The material extruded in step (2) is shaped and cooled to room temperature.
(4)将步骤(3)中定型并冷却后的物料切割,然后进行亚光贴膜处理,从而制得磺酸基生物炭阻燃木塑板。(4) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
上述各实施例中磺酸基生物炭阻燃木塑板的阻燃抑烟作用机理在于热分解过程中组分相互作用发生的化学反应,具体而言,磺化炭的加入不仅能促使CaCO
3分解释放气体CO
2和H
2O,而且能快速促进乙烯-醋酸乙烯树脂、PBS树脂裂解,产生端基为羧酸的产物,该产物与Ca
2+反应形成离子聚合物。入下列各式所示:
The mechanism of flame retardant and smoke suppression of the sulfonic acid-based biochar flame retardant wood-plastic board in the above embodiments lies in the chemical reaction of the interaction of components during the thermal decomposition process. Specifically, the addition of sulfonated carbon can not only promote the CaCO The decomposition releases CO 2 and H 2 O, and can rapidly promote the cracking of ethylene-vinyl acetate resin and PBS resin to produce a product whose end group is carboxylic acid, which reacts with Ca 2+ to form an ionic polymer. Enter the following formulas:
H
++CaCO
3→Ca
2++CO
2↑+H
2O↑
H + +CaCO 3 →Ca 2+ +CO 2 ↑+H 2 O↑
PolymerCOOC
2H
3→PolymerCOOH+CH
2=CH
2↑
PolymerCOOC 2 H 3 →PolymerCOOH+CH 2 =CH 2 ↑
PBS→PolymerCOOH+PolymerC
4H
8OH2 PolymerCOOH+CaCO
3→(PolymerCOO)
2Ca
2++CO
2↑+H
2O↑
PBS→PolymerCOOH+PolymerC 4 H 8 OH2 PolymerCOOH+CaCO 3 →(PolymerCOO) 2 Ca 2+ +CO 2 ↑+H 2 O↑
这些反应的贡献一是在低于温度300℃下,产生可供熔融体系膨胀发泡的气体CO
2和H
2O,而且这些气体具有使火焰自熄的作用。这意味着在更早的阶段形成隔热膨胀型炭层,意义在于可有效增加点燃时间、形成包含Ca化合物的更为耐热的稳定炭层。其次是Ca离子聚合物的形成是一个导致融体交联的过程,交联导致融体黏度增加,有利于稳定热分解初期所形成的膨胀多孔、表层致密的炭结构。还有,磺酸从PVC中夺取氯生成碳正离子,而碳正离子通过Friedel-Crafts反应而发生交联,则减少挥发性烃的生成,在PVC表面形成稳定的炭。所以,磺化炭促进聚合物体系快速成炭,减少可在气相中燃烧的高聚物碎片,同时减少高聚物表面的热量;导热量低的炭层能入射高聚物表面的能量反射出去,因而保护了其下层材料,延缓高聚物的分解及分解产物的挥发。厚实的泡沫炭层的物理结构具有良好的阻燃性能,热释放减少同时,烟气也得到了抑制。
One of the contributions of these reactions is that at a temperature below 300 °C, the gases CO 2 and H 2 O are generated for the expansion and foaming of the molten system, and these gases have the effect of self-extinguishing the flame. This means that the thermally intumescent carbon layer is formed at an earlier stage, which means that the ignition time can be effectively increased and a more heat-resistant stable carbon layer containing the Ca compound can be formed. Secondly, the formation of Ca ion polymer is a process that leads to melt cross-linking. Cross-linking leads to an increase in melt viscosity, which is beneficial to stabilize the expanded porous and dense surface carbon structure formed in the early stage of thermal decomposition. In addition, sulfonic acid abstracts chlorine from PVC to generate carbocations, and carbocations are cross-linked through Friedel-Crafts reaction, which reduces the generation of volatile hydrocarbons and forms stable carbon on the surface of PVC. Therefore, the sulfonated carbon promotes the rapid carbonization of the polymer system, reduces the polymer fragments that can be burned in the gas phase, and reduces the heat on the surface of the polymer; the carbon layer with low thermal conductivity can reflect the energy incident on the surface of the polymer. , thus protecting the underlying material, delaying the decomposition of the polymer and the volatilization of the decomposition products. The physical structure of the thick foam carbon layer has good flame retardant properties, heat release is reduced, and smoke is also suppressed.
富含纤维素、半纤维素、木质素的生物质废弃物,控制炭化条件形成多环芳烃结构,经磺化改性得到磺化炭。磺化炭为黑色颗粒,形状与磺化前没有明显差别,密度、硬度稍微提高,因磺酸基团在炭骨架上的成功构建,吸附性能比木炭更好,且在酸催化反应中均表现出很高的催化活性和较好的稳定性。在聚合物燃 烧过程中,磺酸基团能催化羟基化合物发生脱水成酯、成炭,也可受热分解产生SO
2、CO
2和H
2O而抑制基材燃烧,减少热量释放;同时能有力减少烟雾、CO的排放。可见磺化炭是一种环境友好的阻燃剂或阻燃协效剂。
Biomass wastes rich in cellulose, hemicellulose and lignin, control carbonization conditions to form polycyclic aromatic hydrocarbon structures, and obtain sulfonated carbon through sulfonation modification. The sulfonated carbon is black particles, the shape is not significantly different from that before sulfonation, and the density and hardness are slightly increased. Due to the successful construction of sulfonic acid groups on the carbon skeleton, the adsorption performance is better than that of charcoal, and both perform in acid-catalyzed reactions. high catalytic activity and good stability. In the process of polymer combustion, the sulfonic acid group can catalyze the dehydration of hydroxyl compounds into ester and carbon, and can also be thermally decomposed to generate SO 2 , CO 2 and H 2 O to inhibit the combustion of the substrate and reduce heat release; Reduce smoke and CO emissions. It can be seen that sulfonated carbon is an environmentally friendly flame retardant or flame retardant synergist.
性能与测试Performance and Testing
在对磺酸基生物炭阻燃木塑板(磺化炭/竹木纤维木塑板)进行性能与测试时,所选择的木塑板可来自实施例1-3中制得的其中一个,也可以是发明内容中各组成成分在重量份配比范围中的任意一个组合,在此不做具体限定。In the performance and test of the sulfonic acid-based biochar flame-retardant wood-plastic board (sulfonated carbon/bamboo-wood fiber wood-plastic board), the selected wood-plastic board can be from one of the ones prepared in Examples 1-3, It can also be any combination of the components in the content of the invention in the weight ratio ratio range, which is not specifically limited here.
一、极限氧指数测定1. Determination of Limiting Oxygen Index
极限氧指数(LOI)试验参照《塑料用氧指数法测定燃烧行为》(GB/T 2406.2-2009)进行,样品尺寸为150mm×5mm×5mm。The limiting oxygen index (LOI) test was carried out with reference to "Determination of Combustion Behavior by Oxygen Index Method for Plastics" (GB/T 2406.2-2009), and the sample size was 150mm×5mm×5mm.
根据《建筑内部装修设计防火规范》(GB50222-2017)对单层、多层民用建筑内部各部位装修材料的燃烧性能等级中住宅的阻燃等级最高为B1级,其对应氧指数≥32%。如图1为磺化炭添加量对竹木纤维集成板氧指数的影响规律。由此可知,没添加磺化炭的竹木纤维木塑板的极限氧指数31.8,接近B1级的32。添加0.5%的磺化炭后,竹木纤维集成板的极限氧指数为32.7,超过GB50222-2017的B1级要求。随着磺化炭的添加量增加竹木纤维集成板的极限氧指数增加,当磺化炭添加量增加到2.5%时,极限氧指数为36.1,继续增加到3.0%,极限氧指数为36.0,说明磺化炭继续增加对极限氧指数的影响不再显著,合理的磺化炭添加量在2.5%左右。这说明2.5%的磺化炭能更好地匹配碳酸钙、乙烯-醋酸乙烯树脂、PBS树脂构成的新型膨胀阻燃体系,有利于更好地形成隔热、隔氧的炭层粘附在基材表面,避免了火焰的进一步传播,使火焰自熄。According to the "Code for Fire Protection Design of Interior Decoration of Buildings" (GB50222-2017), the highest flame retardant grade of the residential building is B1, and its corresponding oxygen index is ≥32%. Figure 1 shows the effect of sulfonated carbon addition on the oxygen index of bamboo and wood fiber integrated boards. It can be seen that the limiting oxygen index of the bamboo-wood fiber wood-plastic board without sulfonated carbon is 31.8, which is close to 32 of the B1 level. After adding 0.5% sulfonated carbon, the limiting oxygen index of bamboo-wood fiber integrated board is 32.7, which exceeds the B1 level requirement of GB50222-2017. With the increase of the addition of sulfonated carbon, the limit oxygen index of the bamboo-wood fiber composite board increases. When the addition of sulfonated carbon increases to 2.5%, the limit oxygen index is 36.1, and continues to increase to 3.0%, the limit oxygen index is 36.0, It shows that the effect of the continuous increase of sulfonated carbon on the limiting oxygen index is no longer significant, and the reasonable addition amount of sulfonated carbon is about 2.5%. This shows that 2.5% sulfonated carbon can better match the new intumescent flame retardant system composed of calcium carbonate, ethylene-vinyl acetate resin and PBS resin, which is conducive to better forming a thermal insulation and oxygen barrier carbon layer adhered to the base The surface of the material avoids the further spread of the flame and makes the flame self-extinguishing.
磺化炭/竹木纤维木塑板成型工艺过程中的各因素——主板挤出温度、挤出压力、挤出时间、磺化炭添加百分比为正交试验因素,设计四因素三水平正交试验,考察指标为木塑板抗弯强度、极限氧指数。因素水平表见表1-1,正交实验结果见表1-2,对结果的直观分析见表1-3。Various factors in the forming process of sulfonated carbon/bamboo wood fiber wood-plastic board—the extrusion temperature of the main board, extrusion pressure, extrusion time, and the percentage of sulfonated carbon added are the orthogonal test factors, and the design is orthogonal to four factors and three levels In the test, the inspection indicators are the flexural strength and limiting oxygen index of the wood-plastic board. The factor level table is shown in Table 1-1, the orthogonal experiment results are shown in Table 1-2, and the intuitive analysis of the results is shown in Table 1-3.
表1-1因素水平表Table 1-1 Factor Level Table
表1-2磺化炭/竹木纤维木塑板成型正交实验结果Table 1-2 Orthogonal experimental results of sulfonated carbon/bamboo wood fiber wood-plastic board molding
表1-3结果的直观分析Intuitive analysis of the results in Table 1-3
从表1-2木塑板挤出成型正交试验结果可知,木塑板的抗弯强度在18.8-20.9MPa之间,极限氧指数在33.9-36.5%之间。从结果可知,磺化炭的添加量对极限氧指数和抗弯强度的影响最大,其次是主板挤出温度和挤出压力,最后是挤出时间。From the orthogonal test results of extrusion molding of wood-plastic panels in Table 1-2, it can be seen that the flexural strength of wood-plastic panels is between 18.8-20.9MPa, and the limiting oxygen index is between 33.9-36.5%. It can be seen from the results that the addition amount of sulfonated carbon has the greatest influence on the limiting oxygen index and flexural strength, followed by the extrusion temperature and extrusion pressure of the main plate, and finally the extrusion time.
从实验结果看,试验2水平组合为A
1B
2C
2D
2、试验3水平组合为A
1B
3C
3D
3、试验6水平组合为A
2B
3C
1D
2都有较好的抗弯强度和极限氧指数。
From the experimental results, the level combination of test 2 is A 1 B 2 C 2 D 2 , the level combination of test 3 is A 1 B 3 C 3 D 3 , and the level combination of test 6 is A 2 B 3 C 1 D 2 . flexural strength and limiting oxygen index.
在正交试验的基础上,进一步对木塑板挤出成型条件进行单因素优化。从表1-4中数据看,主板挤出温度对木塑板抗弯强度的影响随温度升高而升高后又降低,综合其对极限氧指数的影响,最佳的挤出温度为174℃。On the basis of the orthogonal test, the single factor optimization of the extrusion molding conditions of the wood-plastic board was further carried out. From the data in Table 1-4, the influence of the extrusion temperature of the main board on the flexural strength of the wood-plastic board increases and then decreases with the increase of the temperature. Combining its influence on the limiting oxygen index, the optimal extrusion temperature is 174 °C.
选择主板挤出温度(即上述实施例中的螺杆挤出机中的加工温度)为174℃,考察挤出压力对抗弯强度和极限氧指数的影响规律。从表1-5可知,随压力的增加,抗弯强度增加,但是当压力为8.0-8.5MPa时,其极限氧指数有较高值。因此8.0MPa是比较合适的挤出压力。The extrusion temperature of the main plate (ie the processing temperature in the screw extruder in the above embodiment) was selected to be 174°C, and the influence of extrusion pressure on the bending strength and limiting oxygen index was investigated. It can be seen from Table 1-5 that with the increase of pressure, the flexural strength increases, but when the pressure is 8.0-8.5MPa, the limit oxygen index has a higher value. Therefore, 8.0MPa is a more suitable extrusion pressure.
确定主板挤出温度为174℃,挤出压力为8.0MPa。而随着时间的延长,木塑板的抗弯强度和极限氧指数增加,选择挤出时间60s较为合适(如表1-6所示)。The extrusion temperature of the main board was determined to be 174°C, and the extrusion pressure was determined to be 8.0 MPa. With the extension of time, the flexural strength and limiting oxygen index of the wood-plastic board increase, and it is more appropriate to choose the extrusion time of 60s (as shown in Table 1-6).
表1-4主板挤出温度对木塑板的对抗弯强度和极限氧指数影响Table 1-4 Influence of extrusion temperature of main board on flexural strength and limiting oxygen index of wood-plastic board
表1-5主板挤出压力对木塑板的对抗弯强度和极限氧指数影响Table 1-5 Influence of extrusion pressure of main board on flexural strength and limiting oxygen index of wood-plastic board
表1-6挤出时间对木塑板的对抗弯强度和极限氧指数影响Table 1-6 Influence of extrusion time on flexural strength and limiting oxygen index of wood-plastic panels
二、热重分析2. Thermogravimetric analysis
采用TGA-Q500热重分析仪测试磺化炭/竹木纤维木塑板的热降解性能。称取8~12mg干燥粉末,在10℃/min升温速率下由40℃加热至800℃。保护气体为高纯氮气,流量20mL/min。The thermal degradation performance of sulfonated carbon/bamboo wood fiber wood-plastic board was tested by TGA-Q500 thermogravimetric analyzer. Weigh 8-12 mg of dry powder and heat it from 40°C to 800°C at a heating rate of 10°C/min. The protective gas is high-purity nitrogen with a flow rate of 20 mL/min.
不同添加量磺化炭的竹木纤维集成板在氮气氛围下的热失重曲线与数据分 别如图2、表2所示。从曲线可知,磺化炭的加入没有明显改变竹木纤维集成板的热解曲线形状,但是随着磺化炭的增加,竹木纤维集成板的降解速率减缓,燃烧剩余物提高,尤其是500℃以上高温区,剩余物的热稳定性明显增加。The thermogravimetric curves and data of bamboo-wood fiber integrated boards with different amounts of sulfonated carbon under nitrogen atmosphere are shown in Figure 2 and Table 2, respectively. It can be seen from the curve that the addition of sulfonated carbon did not significantly change the shape of the pyrolysis curve of the bamboo-wood fiber integrated board, but with the increase of sulfonated carbon, the degradation rate of the bamboo-wood fiber integrated board slowed down and the combustion residue increased, especially the 500 In the high temperature region above ℃, the thermal stability of the residue increases significantly.
表2不同竹木纤维集成板的热失重数据Table 2 Thermal weight loss data of different bamboo and wood fiber integrated boards
所有试样降解5%的温度T
5%相差不大,但是试样降解50%时的T
50%就显著不同,没添加磺化炭的S-0.0%,其T
50%是734.2℃,随着磺化炭的增加,T
50%升高,S-2.5%的是771.3℃,比S-0.0%的提高了37.1℃。从400℃、600℃、800℃对应的降解剩余物可知,无磺化炭的S-0.0%的剩余物质量百分率最低分别为74.07%、60.39%、31.46%;添加0.5%的S-0.5%试样,对应的剩余物质量百分率分别比S-0.0%增加2.21%、3.10%、4.11%;随着磺化炭的增加,高温下的降解剩余物越来越多,当添加2.5%时,试样S-2.5%在400℃、600℃、800℃剩余物质量百分率分别是77.30%、68.48%、45.66%,比S-0.0%试样相应增加3.23%、8.09%、14.2%,实验结果表明,磺化炭的加入迅速提高了试样在高温(400-800℃)区间的热稳定性能,这是磺化炭催化了碳酸钙、乙烯-醋酸乙烯树脂、PBS树脂体系受热形成了更好的炭层屏障,能高效隔绝热、氧气,保护下层基材。
The temperature T 5% of all samples degraded by 5% is not different, but the T 50% of the samples degraded by 50% is significantly different. For S-0.0% without sulfonated carbon, the T 50% is 734.2 ℃, with With the increase of sulfonated carbon, T 50% increased, S-2.5% was 771.3℃, which was 37.1℃ higher than S-0.0%. From the degradation residues corresponding to 400°C, 600°C, and 800°C, it can be seen that the lowest mass percentage of S-0.0% without sulfonated carbon is 74.07%, 60.39%, and 31.46%, respectively; adding 0.5% of S-0.5% For the sample, the corresponding residual mass percentages increased by 2.21%, 3.10% and 4.11% respectively compared with S-0.0%; with the increase of sulfonated carbon, the degradation residues at high temperature became more and more, when adding 2.5%, The mass percentages of sample S-2.5% at 400 °C, 600 °C, and 800 °C are 77.30%, 68.48%, and 45.66%, respectively, which are 3.23%, 8.09%, and 14.2% higher than that of the S-0.0% sample. The experimental results It shows that the addition of sulfonated carbon rapidly improves the thermal stability of the sample in the high temperature range (400-800 °C), which is because the sulfonated carbon catalyzes the formation of better calcium carbonate, ethylene-vinyl acetate resin and PBS resin systems when heated. The carbon layer barrier can effectively isolate heat and oxygen, and protect the underlying substrate.
三、燃烧性能评价3. Evaluation of combustion performance
参照ISO5660-1标准,采用英国FTT锥形量热仪测量磺化炭/竹木纤维木塑板的燃烧性能。试件尺寸为100mm×100mm×10mm(长×宽×厚)。按ISO5660-1-2002标准,将锥形量热仪CONE试样除受热面外的所有面用铝箔纸包裹,放入不锈钢样品架中,在铝箔底部阻隔热传递,在50kW·m
-2热辐照功率下对样品进行***研究测试时,材料表面温度约为760℃。
Referring to the ISO5660-1 standard, the British FTT cone calorimeter was used to measure the combustion performance of the sulfonated carbon/bamboo wood fiber wood-plastic board. The size of the test piece is 100mm×100mm×10mm (length×width×thickness). According to the ISO5660-1-2002 standard, wrap all surfaces of the CONE sample of the cone calorimeter except the heated surface with aluminum foil, put it in a stainless steel sample holder, block heat transfer at the bottom of the aluminum foil, and heat it at 50kW·m -2 The surface temperature of the material was about 760°C when the samples were systematically studied and tested under irradiation power.
热释放速率HRR是表征火灾强度的最重要的参数,是指在预先设置的辐射强度下,材料燃烧时单位面积的热释放速率。HRR或者是PHRR越大,单位时间内单位面积材料燃烧反馈的热量越多,这就导致材料热解速度加快、挥发性可燃气体产量增加,火灾传播速度加快。所以,HRR或PHRR越大,材料在火灾中的危险性越大。总热释放量(Total Heat Release,简称THR),是指在预先设置的热辐射强度下,从材料点燃到火熄灭之间所释放出的热量的综合,THR=∫HRRdt,其单位是MJ/m
2。THR越大,材料燃烧释放出的热量越多,造成的危害越大。HRR与THR结合起来,可以客观全面来评价材料的燃烧性能。
The heat release rate HRR is the most important parameter to characterize the fire intensity, which refers to the heat release rate per unit area when the material burns under the preset radiation intensity. The larger the HRR or PHRR is, the more heat is fed back from the combustion of the material per unit area per unit time, which leads to faster pyrolysis of the material, increased production of volatile combustible gases, and faster fire spread. Therefore, the greater the HRR or PHRR, the greater the risk of the material in fire. Total Heat Release (THR) refers to the synthesis of the heat released between the ignition of the material and the extinguishment of the fire under the preset thermal radiation intensity, THR=∫HRRdt, and its unit is MJ/ m 2 . The higher the THR, the more heat the material releases when it burns, and the more damage it causes. The combination of HRR and THR can objectively and comprehensively evaluate the combustion performance of materials.
不同竹木纤维集成板的CONE实验数据列于表3-1,图3、4分别为不同竹木纤维集成板的热释放速率曲线和总热释放量曲线。未添加磺化炭的S-0.0%试样,点燃时间TTI(time to ignition)是30s,火焰熄灭时间FET(flame extinction time)317s,有焰燃烧时间为287s;随着磺化炭的加入,试样点燃时间增加,熄灭时间提前,其中试样S-2.0%、S-2.5%的TTI最长,为35s,FET最早,为190s,有焰燃烧时间为155s,比S-0.0%减少了132s的明火燃烧。从CONE实验的热释放数据可知,磺化炭的加入能有效地减少热量释放。S-2.5%的最高热释放速率峰值PHRR比S-0.0%的168.3kW/m
2降低了16.7%,平均热释放速率MHRR、有效燃烧EHC分别为70.30kW/m
2、11.30MJ/kg,比S-0.0%的95.30kW/m
2分别减少了25.00kW/m
2、2.79MJ/kg,为26.2%、19.8%;S-2.5%的总热释放量THR为19.24MJ/m
2,比S-0.0%的THR38.13MJ/m
2减少了49.5%。由图3、4的不同竹木纤维集成板的热释放速率曲线和总热释放量曲线可看出,磺化炭加入明显减小了热释放速率和总热释放量,尤其是试样S-2.5%的曲线最明显,处在其他试样曲线下方。火灾蔓延指数(FGI)是热释放速率峰值(PHRR)和到达峰值时间(t
PHRR)的比值。FGI越大,表明达到一个较高热释放速率峰值所用时间越短,则火灾危险性越大。从表3-1可知,S-0.0%的FGI为4.04kw/s.m
2,随着磺化炭的增加,FGI依次减小,S-2.5%的FGI1.02kw/s.m
2,不到S-0.0%FGI的四分之一。说明磺化炭的加入能有效抑制竹木纤维木塑板的热量释放,减小火焰传播,降低火灾危险性。
The CONE experimental data of different bamboo and wood fiber integrated boards are listed in Table 3-1. Figures 3 and 4 are the heat release rate curves and total heat release curves of different bamboo and wood fiber integrated boards, respectively. For the S-0.0% sample without sulfonated carbon, the ignition time TTI (time to ignition) is 30s, the flame extinction time FET (flame extinction time) is 317s, and the flame burning time is 287s; with the addition of sulfonated carbon, The ignition time of the samples increases, and the extinction time is advanced. Among them, the TTI of the samples S-2.0% and S-2.5% is the longest, which is 35s, the FET is the earliest, which is 190s, and the flame burning time is 155s, which is shorter than that of S-0.0%. 132s of open flame burning. From the heat release data of the CONE experiment, it can be seen that the addition of sulfonated carbon can effectively reduce the heat release. The peak PHRR of the highest heat release rate of S-2.5% is 16.7% lower than that of S-0.0%, which is 168.3kW/m 2 . The average heat release rate MHRR and the effective combustion EHC are 70.30kW/m 2 and 11.30MJ/kg, respectively. The 95.30kW/m 2 of S-0.0% is reduced by 25.00kW/m 2 and 2.79MJ/kg, respectively, which are 26.2% and 19.8% ; -0.0% THR38.13MJ/m 2 decreased by 49.5%. From the heat release rate curves and total heat release curves of different bamboo-wood fiber integrated boards in Figures 3 and 4, it can be seen that the addition of sulfonated carbon significantly reduces the heat release rate and total heat release, especially for the sample S- The 2.5% curve is the most obvious and is below the curve of the other samples. The Fire Spread Index (FGI) is the ratio of the peak heat release rate (PHRR) to the time to peak (t PHRR ). The larger the FGI, the shorter the time it takes to reach a higher peak heat release rate and the greater the fire hazard. It can be seen from Table 3-1 that the FGI of S-0.0% is 4.04kw/sm 2 . With the increase of sulfonated carbon, the FGI decreases in turn. The FGI of S-2.5% is 1.02kw/sm 2 , less than S-0.0 A quarter of %FGI. It shows that the addition of sulfonated carbon can effectively inhibit the heat release of bamboo and wood fiber wood-plastic panels, reduce the spread of flames, and reduce the risk of fire.
表3-1不同竹木纤维集成板的锥形量热数据Table 3-1 Cone calorimetry data of different bamboo and wood fiber integrated boards
火灾中烟雾与毒气是造成人员伤亡的主要原因。有毒气体导致人员窒息,烟雾降低火场中的能见度,妨碍消防人员进入火灾现场进行抢救,使火灾现场的人员难于疏散和逃离。据统计,火灾死亡人数中有70~80%是由于烟和有毒气体窒息造成的。因此,烟和有毒气体是火灾中导致人员伤亡的重要因素。不同竹木纤维集成板的CONE烟气数据如表3-2所示,总烟释放量曲线见图5。从表3-2可知,因为原料中的PVC燃烧时,会释放出大量的烟雾,所以S-0.0%的烟气释放速率SPR高达1381.8m
2/s,总烟释放量为TSP12.29m
2/m
2,是所有试样中最高的。磺化炭的加入能迅速降低烟气释放速率及总烟释放量,1.5%的添加已经使SPR降至689.2m
2/s,比S-0.0%减少一半以上。磺化炭的增加,使得SPR和TSP进一步降低,S-2.5%的SPR降至486.4m
2/s,仅为S-0.0%的35.2%;TSP为4.99m
2/m
2,比S-0.0%减少了7.3m
2/m
2,约59.4%。CO是火灾中引起人员窒息和中毒的最主要因素,而磺化炭的加入能高效降低一氧化碳的产量,2.5%的添加量使得一氧化碳的产量由45.5g/kg减少到21.4g/kg,减少了53.0%。CO的减少除了磺化炭的多孔结构对烟雾的吸附,主要是磺化炭对竹木纤维体系的催化成炭,迅速成炭的成炭速率和优良的成炭质量使得炭层下的试样被高效保护,火焰更快熄灭,燃烧时间缩短。
Smoke and poisonous gas are the main causes of casualties in fires. Toxic gas causes people to suffocate, smoke reduces visibility in the fire scene, prevents firefighters from entering the fire scene for rescue, and makes it difficult for people at the fire scene to evacuate and escape. According to statistics, 70% to 80% of fire deaths are caused by smoke and toxic gas suffocation. Therefore, smoke and toxic gases are important factors that cause casualties in fires. The CONE smoke data of different bamboo and wood fiber integrated boards are shown in Table 3-2, and the total smoke emission curve is shown in Figure 5. From Table 3-2, it can be seen that when the PVC in the raw material is burned, a large amount of smoke will be released, so the smoke release rate SPR of S-0.0% is as high as 1381.8m 2 /s, and the total smoke release amount is TSP12.29m 2 / m 2 , the highest among all samples. The addition of sulfonated carbon can quickly reduce the rate of flue gas release and the total amount of smoke released. The addition of 1.5% has reduced the SPR to 689.2m 2 /s, which is more than half of that of S-0.0%. With the increase of sulfonated carbon, SPR and TSP are further reduced, SPR of S-2.5% is reduced to 486.4m 2 /s, only 35.2% of S-0.0%; TSP is 4.99m 2 /m 2 , which is lower than that of S-0.0 % decreased by 7.3m 2 /m 2 , about 59.4%. CO is the most important factor causing suffocation and poisoning in fires. The addition of sulfonated carbon can effectively reduce the production of carbon monoxide. The addition of 2.5% reduces the production of carbon monoxide from 45.5g/kg to 21.4g/kg. 53.0%. In addition to the adsorption of smog by the porous structure of the sulfonated carbon, the reduction of CO is mainly due to the catalytic carbonization of the bamboo-wood fiber system by the sulfonated carbon. The rapid carbonization rate and excellent carbonization quality make the samples under the carbon layer Being efficiently protected, the flame goes out faster and the burning time is shortened.
表3-2不同竹木纤维集成板的锥形量热数据Table 3-2 Cone calorimetry data of different bamboo and wood fiber integrated boards
四、磺化炭/竹木纤维木塑板的残余物形貌分析4. Morphology analysis of residues of sulfonated carbon/bamboo wood fiber wood-plastic board
采用FEI公司的Quanta 450型环境扫描电镜,观察磺化炭/竹木纤维木塑板燃烧后的形貌。测试前,对试件进行表面喷金处理。Using the Quanta 450 environmental scanning electron microscope of FEI Company, the morphology of the sulfonated carbon/bamboo wood fiber wood-plastic board after combustion was observed. Before the test, the surface of the specimen was sprayed with gold.
竹木纤维集成板的电镜照片如图6,从图可知,无添加磺化炭的S-0.0%的残炭孔洞多而大小不一,且孔洞深邃,残炭表面类粉末状,没连成整体。加入磺化炭后,试样残炭表面变化明显,S-0.5%的孔洞减少,但个别孔洞还是较深;随着磺化炭的增加,S-1.0%、S-1.5%、S-2.0%、S-2.5%的孔洞逐渐减少,且孔洞的均匀性增加,炭层的整体性、致密性越来越好。对比S-0.0%、S-2.5%的1.0KX放大倍数残炭(如图7所示)更进一步发现,磺化炭加入改变了S-0.0%大量的脆裂状的炭层,有利于试样形成较大块的炭,把整个炭层绵延成一个裂纹极少的致密整体。这种坚实的炭层结构成为保护下层材料的屏障,能高效隔绝热量、氧气,有效抑制下层材料燃烧,减少热量、烟气产生。The electron microscope photo of the bamboo-wood fiber integrated board is shown in Figure 6. It can be seen from the figure that the S-0.0% carbon residue without sulfonated carbon has many pores and different sizes, and the pores are deep, and the surface of the carbon residue is powdery and not connected. overall. After adding sulfonated carbon, the surface of the sample carbon residue changed obviously, the pores of S-0.5% decreased, but the individual pores were still deep; with the increase of sulfonated carbon, S-1.0%, S-1.5%, S-2.0 % and S-2.5% pores gradually decrease, and the uniformity of pores increases, and the integrity and compactness of the carbon layer are getting better and better. Comparing S-0.0% and S-2.5% carbon residues at 1.0KX magnification (as shown in Figure 7), it is further found that the addition of sulfonated carbon changes a large amount of brittle carbon layers in S-0.0%, which is beneficial to the test. In this way, larger pieces of carbon are formed, and the entire carbon layer stretches into a dense whole with few cracks. This solid carbon layer structure becomes a barrier to protect the underlying material, which can efficiently isolate heat and oxygen, effectively inhibit the combustion of the underlying material, and reduce the generation of heat and smoke.
上述实施方式提供的磺酸基生物炭阻燃木塑板符合T/CADBM3-2018《竹木纤维集成墙板》、GB18580-2017《室内装饰材料人造板及其制品中甲醛释放量》、《2020湖南省装饰板类产品质量监督抽查实施细则(HNCCXZ131-2020)》要求;阻燃性能达到《建筑材料及制品燃烧性能分级》(GB 8624-2012)B1等级要求。磺化炭/竹木纤维木塑板(即磺酸基生物炭阻燃木塑板)产品及其制备工艺绿色环保,是人们绿色家居的理想材料。The sulfonic acid-based biochar flame-retardant wood-plastic board provided by the above embodiment complies with T/CADBM3-2018 "Bamboo and Wood Fiber Integrated Wallboard", GB18580-2017 "Formaldehyde Release in Wood-based Panels of Interior Decoration Materials and Their Products", "2020" The implementation rules for quality supervision and random inspection of decorative panel products in Hunan Province (HNCCXZ131-2020) requirements; the flame retardant performance meets the requirements of the B1 level of the "Classification of Combustion Performance of Building Materials and Products" (GB 8624-2012). The sulfonated carbon/bamboo wood fiber wood-plastic board (ie, sulfonic acid-based biochar flame-retardant wood-plastic board) product and its preparation process are green and environmentally friendly, and are ideal materials for people's green homes.
从我国木材的需求量来看,木材供需矛盾尖锐,对木材剩余物的增值开发技术需求巨大。从家居等建筑材料的需求来看,因木塑复合材料具有可刨可锯、可钉可钻、浸水不胀、干燥不裂、防蛀耐腐、零醛无毒无味的性能优势,其本身亦可回收利用,是名副其实的环境友好型绿色材料,在诸多领域应用前景巨大。市场对绿色生产的绿色WPC需求量将越来越大。Judging from the demand for wood in my country, the contradiction between supply and demand of wood is acute, and there is a huge demand for value-added development technologies for wood residues. From the perspective of the demand for building materials such as home furnishing, wood-plastic composite materials have the performance advantages of planing and sawing, nailing and drilling, water immersion, non-swelling, drying and cracking, moth-proof and corrosion-resistant, zero aldehyde, non-toxic and tasteless. It can also be recycled. It is a veritable environment-friendly green material and has great application prospects in many fields. The market demand for green WPC for green production will increase.
磺化炭/竹木纤维木塑板产品具有良好的功能性和市场应用前景,其生产技术可以完全在传统的木塑板生产线上进行产业升级,其产品与传统的木塑板相比具有环保、阻燃、轻质高强等功能性优势。Sulfonated carbon/bamboo fiber wood-plastic board products have good functionality and market application prospects. Its production technology can be completely upgraded in the traditional wood-plastic board production line. Compared with traditional wood-plastic boards, its products are environmentally friendly. , flame retardant, light weight and high strength and other functional advantages.
上述实施例为本公开较佳的实现方案,除此之外,本公开还可以其它方式实现,在不脱离本技术方案构思的前提下任何显而易见的替换均在本公开的保护范围之内。The above-mentioned embodiment is a preferred implementation solution of the present disclosure. In addition, the present disclosure can also be implemented in other ways, and any obvious replacements are within the protection scope of the present disclosure without departing from the concept of the technical solution.
为了让本领域普通技术人员更方便地理解本公开相对于现有技术的改进之处,本公开的一些附图和描述已经被简化,并且为了清楚起见,本申请文件还省略了一些其它元素,本领域普通技术人员应该意识到这些省略的元素也可构成本公开的内容。In order to make it easier for those skilled in the art to understand the improvements of the present disclosure over the prior art, some drawings and descriptions of the present disclosure have been simplified, and for the sake of clarity, some other elements are also omitted in this application document, One of ordinary skill in the art would appreciate that such omitted elements may also constitute the subject matter of the present disclosure.
Claims (4)
- 一种磺酸基生物炭阻燃木塑板,包括以下重量份配比的组成成分:竹木纤维粉20-30份,重质碳酸钙90-110份,聚氯乙烯树脂粉70-90份,PBS树脂9-15份,空心陶瓷微珠8-12份,乙烯-醋酸乙烯共聚物8-12份,磺化炭5.5-7.5份,热稳定剂4-5份,发泡调节剂5-6份,发泡剂0.6-1.2份,硬脂酸0.5-1份,PE蜡0.5-1份。A sulfonic acid-based biochar fire-retardant wood-plastic board, comprising the following components in parts by weight: 20-30 parts of bamboo and wood fiber powder, 90-110 parts of heavy calcium carbonate, and 70-90 parts of polyvinyl chloride resin powder , 9-15 parts of PBS resin, 8-12 parts of hollow ceramic beads, 8-12 parts of ethylene-vinyl acetate copolymer, 5.5-7.5 parts of sulfonated carbon, 4-5 parts of heat stabilizer, 5- 6 parts, 0.6-1.2 part of foaming agent, 0.5-1 part of stearic acid, 0.5-1 part of PE wax.
- 根据权利要求1所述的磺酸基生物炭阻燃木塑板,其中:所述竹木纤维粉为处理成干燥状态的竹木纤维粉。The sulfonic acid-based biochar fire-retardant wood-plastic board according to claim 1, wherein: the bamboo and wood fiber powder is processed into a dry state.
- 一种生产如权利要求2所述的磺酸基生物炭阻燃木塑板的方法,其中,包括以下步骤:A method for producing the sulfonic acid-based biochar fire-retardant wood-plastic board as claimed in claim 2, wherein, comprising the following steps:(1)将竹木纤维粉、重质碳酸钙、聚氯乙烯树脂粉、PBS树脂、空心陶瓷微珠、乙烯醋酸乙烯共聚物、磺化炭、热稳定剂、发泡调节剂、发泡剂、硬脂酸、PE蜡按照所述重量份配比混合搅拌均匀并塑化,得到混匀物;(1) Combine bamboo and wood fiber powder, heavy calcium carbonate, polyvinyl chloride resin powder, PBS resin, hollow ceramic microbeads, ethylene vinyl acetate copolymer, sulfonated carbon, heat stabilizer, foaming regulator, foaming agent , stearic acid and PE wax are uniformly mixed and plasticized according to the proportion by weight to obtain a mixture;(2)将步骤(1)中得到的混匀物加入到螺杆挤出机中进行挤出成型;(2) adding the blend obtained in the step (1) into the screw extruder for extrusion molding;(3)使步骤(2)中挤出成型的物料定型并冷却至室温;(3) making the material extruded in step (2) stereotyped and cooled to room temperature;(4)将步骤(3)中定型并冷却后的物料切割,然后进行亚光贴膜处理,从而制得磺酸基生物炭阻燃木塑板。(4) Cutting the shaped and cooled material in step (3), and then carrying out a matte filming treatment to obtain a sulfonic acid-based biochar fire-retardant wood-plastic board.
- 根据权利要求3所述的生产磺酸基生物炭阻燃木塑板的方法,其中:在步骤(2)的螺杆挤出机中的加工温度为170~180℃。The method for producing a sulfonic acid-based biochar fire-retardant wood-plastic board according to claim 3, wherein: the processing temperature in the screw extruder in step (2) is 170-180°C.
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CN114644333A (en) * | 2022-03-17 | 2022-06-21 | 湖南恒信新型建材有限公司 | Preparation method of sulfonated carbon for thermal cracking aromatization of biomass at constant temperature and temperature |
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