CN112223465A - Halogen-free multi-effect wood fire retardant and preparation method thereof - Google Patents

Halogen-free multi-effect wood fire retardant and preparation method thereof Download PDF

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Publication number
CN112223465A
CN112223465A CN202011140912.0A CN202011140912A CN112223465A CN 112223465 A CN112223465 A CN 112223465A CN 202011140912 A CN202011140912 A CN 202011140912A CN 112223465 A CN112223465 A CN 112223465A
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halogen
parts
flame
ammonium polyphosphate
fire retardant
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郭熙焕
吉桂平
刘海霞
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Rugao Fuqiang Flame Retardant Co ltd
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Rugao Fuqiang Flame Retardant Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/007—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/163—Compounds of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/166—Compounds of phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/343—Heterocyclic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/20—Removing fungi, molds or insects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

The invention discloses a halogen-free multi-effect wood fire retardant and a preparation method thereof, and the preparation raw materials comprise, by weight, 70-99 parts of a fire retardant component, 1-3 parts of a moisture-resistant agent, 1-3 parts of an antirust agent, 1-3 parts of a mildew preventive, 1-2 parts of a quick drying agent and 1-5 parts of a nano oxide. The flame retardant provided by the invention is low in cost, does not contain halogen, is more environment-friendly, and has excellent flame retardance, mildew resistance, rust resistance and quick drying capability.

Description

Halogen-free multi-effect wood fire retardant and preparation method thereof
Technical Field
The invention belongs to the field of wood flame retardants, and particularly relates to a halogen-free multi-effect wood flame retardant and a preparation method thereof.
Background
The wood has the advantages of high strength-weight ratio, rich and beautiful texture and color, excellent environmental characteristics, easy processing and the like, and is widely applied to the fields of furniture, interior decoration, buildings and the like. The wood is flammable biomass material, and can reach the flame retardant level of the public place decoration material required by mandatory national standards only by flame retardant treatment.
Currently, commercially available flame retardants for use in wood are broadly classified into organic and inorganic types according to their categories. The conventional flame retardant with single flame-retardant effect cannot meet the requirement, the organic flame retardant has the advantages of stable molecular group structure, low moisture regain and migration resistance, the produced flame-retardant wood is not easy to breed mould, has low corrosion to metal and the like, but has poor biodegradability, is not very friendly to the environment, has high raw material cost and cannot be accepted by the market; although the inorganic flame retardant is low in cost, the inorganic flame retardant adopts strong acid weak base salt or weak acid weak base salt, so that the metal pressure tank body is strongly corroded during use, the service life of the pressure tank is shortened, and the produced flame-retardant wood is easy to regain moisture and migrate, is easy to breed mold and strongly corrodes metal components. In addition, in the large-scale production of the flame-retardant wood, a full cell method or a normal-pressure soaking method is generally adopted, the treated wood is aired or dried, the airing field is dozens of acres in a small quantity, and the airing field is hundreds of acres in a large quantity, if the airing drying speed can be increased, the airing field can be greatly saved, the turnover speed of the wood can be increased, and the work efficiency can be improved.
Disclosure of Invention
In order to solve the problems, the invention provides a halogen-free multi-effect wood fire retardant, which comprises, by weight, 70-99 parts of a fire retardant component, 1-3 parts of a moisture-resistant agent, 1-3 parts of an antirust agent, 1-3 parts of a mildew preventive, 1-2 parts of a quick drying agent and 1-5 parts of a nano oxide.
As a preferable technical scheme, the flame-retardant component is one or a mixture of more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium polyphosphate, borax, urea phosphate, ammonium sulfate, dicyandiamide, ammonium bicarbonate, sulfamate, borate and melamine in any proportion.
As a preferable technical scheme, the flame retardant component is a mixture of ammonium polyphosphate, borax and melamine.
As a preferable technical scheme, the weight ratio of ammonium polyphosphate, borax and melamine is (8-12): (1-3): 1.
as a preferable technical scheme, the ammonium polyphosphate is type II ammonium polyphosphate, and the polymerization degree is not less than 1000.
As a preferable technical scheme, the type II ammonium polyphosphate is modified by gamma-aminopropyltriethoxysilane, and the modification method is as follows:
s1, mixing gamma-aminopropyltriethoxysilane, ethanol and distilled water according to the volume ratio of 2: 10: putting the mixture into a three-necked bottle according to the proportion of 1, performing water bath reaction at the temperature of 45 ℃ for 1 hour, and adjusting the pH value to be 4-5 to obtain a modifier;
s2, adding a certain amount of type II ammonium polyphosphate into 120mL of ethanol, wherein the weight ratio of the amount of the type II ammonium polyphosphate to the amount of the gamma-aminopropyltriethoxysilane in the S1 is (18-22): 1, ultrasonically dispersing for 30min, heating in water bath to 60 ℃, adding the modifier in S1, stirring for 1h at the constant temperature of 60 ℃, carrying out suction filtration, and drying a sample in a drying oven at the temperature of 60 ℃ to obtain white powder, namely the modified type II ammonium polyphosphate.
As a preferable technical scheme, the quick drying agent is a mixture of an infrared absorbent and magnesium hydroxide, and the weight ratio is (0.8-1.2): 1.
as a preferred technical scheme, the nano oxide is nano SiO2And nano TiO2The weight ratio of (5-8) to 1, and the nano SiO2The specific surface area of (A) is 200 to 300m2/g。
As a preferred technical scheme, the nano SiO2And nano TiO2The average particle diameter of (B) is 10 to 50 nm.
The invention provides a preparation method of a halogen-free multi-effect wood fire retardant, which comprises the following steps: adding the flame-retardant component and the moisture-resistant agent into a horizontal mixing kettle according to the proportion, stirring for 20-40 minutes at the speed of 30-50 rpm, adding the antirust agent, the mildew-proof agent, the quick-drying agent and the nano oxide, mixing for 80-100 minutes, and discharging to obtain the flame retardant.
Has the advantages that:
1. the flame retardant component is the mixture of ammonium polyphosphate, borax and melamine, so that the flame retardant is prevented from only having a single flame retardant effect.
2. The weight ratio of ammonium polyphosphate, borax and melamine is (8-12): (1-3): 1 hour, the charcoal layer surface after fire-retardant sample burning is even porous honeycomb structure, and is more level and smooth, can reduce the quiet bending strength of plank to the maximize to slowed down the propagation speed of flame, further improved fire behaviour.
3. The ammonium polyphosphate is II type ammonium polyphosphate, has polymerization degree not less than 1000, has higher carbon forming rate, can form a net structure, improves P-N synergistic action, is favorable for forming a protective film on the surface of wood with a mildew inhibitor and an anti-embroidery agent, and improves mildew-proof, anti-embroidery and anti-corrosion capabilities.
4. The modified II-type polyphosphoric acid II improves the compatibility and the mechanical property of wood, and also improves the anti-embroidery and anti-corrosion capabilities of the flame retardant.
5. Nano SiO2And nano TiO2The weight ratio of (5-8) to (1) of nano SiO2The specific surface area of (A) is 200 to 300m2Per g, increased nano SiO2And nano TiO2The compatibility and the binding force with the flame-retardant wood further improve the flame-retardant capability and the antibacterial, mildewproof and antirust capability of the flame-retardant wood.
Drawings
Fig. 1 shows the appearance of the flame-retardant wood obtained in example 1 after the mildew-proof and rust-proof tests.
Fig. 2 is a shape of the flame-retardant wood obtained in comparative example 2 after the mildewproof and rustproof tests.
Fig. 3 is a shape of the flame-retardant wood obtained in comparative example 3 after the mildewproof and rustproof tests.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present disclosure, the definition of the term provided in the present disclosure controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present invention, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the problems, the first aspect of the invention provides a halogen-free multi-effect wood fire retardant, which comprises, by weight, 70-99 parts of a fire retardant component, 1-3 parts of a moisture-resistant agent, 1-3 parts of an antirust agent, 1-3 parts of a mildew preventive, 1-2 parts of a quick drying agent and 1-5 parts of a nano oxide.
In some preferred embodiments, the flame retardant component is selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium polyphosphate, borax, urea phosphate, ammonium sulfate, dicyandiamide, ammonium bicarbonate, sulfamate, borate and melamine which are mixed in any proportion.
In order to avoid that the flame retardant has only a single flame retarding effect, in some preferred embodiments the flame retardant component is a blend of ammonium polyphosphate, borax, melamine. The combined water contained in borax can absorb a large amount of heat, and the heat insulation and oxygen resistance stability of the porous carbon foam layer formed on the surface of wood by ammonium polyphosphate is improved. The oxygen concentration and the combustible gas concentration of the porous carbon foam layer formed on the surface of the wood by the ammonium polyphosphate are reduced by the non-combustible gas generated after the melamine is decomposed, and the flame retardant capability of the ammonium polyphosphate is improved. In addition, the oxide generated after the melamine is decomposed traps free radicals in the wood, so that the combustion of the wood is inhibited, and the generation of molten drops of the porous carbon foam layer is also inhibited.
In some more preferred embodiments, the inventors surprisingly found that when the weight ratio of ammonium polyphosphate, borax and melamine is (8-12): (1-3): 1 hour, the charcoal layer surface after fire-retardant sample burning is even porous honeycomb structure, and is more level and smooth, can reduce the quiet bending strength of plank to the maximize to slowed down the propagation speed of flame, further improved fire behaviour.
In some preferred embodiments, the ammonium polyphosphate is type II ammonium polyphosphate, has a polymerization degree of not less than 1000, has a higher carbon forming rate, can form a net structure, improves the P-N synergistic effect, is favorable for forming a protective film on the surface of wood with a mildew inhibitor and an anti-embroidery agent, and improves the mildew-proof, anti-embroidery and anti-corrosion capabilities. In addition, the combination of borax, ammonium sulfate and wood can be stabilized, and the loss rate of the flame-retardant components is reduced, so that the combustion rate and the heat release amount of the wood are reduced, and the flame-retardant capability is improved.
In order to improve the compatibility of the type ii ammonium polyphosphate and the mechanical properties of wood, in some more preferred embodiments, the type ii ammonium polyphosphate is gamma-aminopropyltriethoxysilane modified type ii ammonium polyphosphate. Through modification, part of ammonium polyphosphate generates phosphoric acid, and an acidic group and a siloxane group generated by gamma-aminopropyltriethoxysilane generate a crosslinking esterification reaction, so that on one hand, the surface of modified type II ammonium polyphosphate is successfully grafted with an organic group, the compatibility of the type II ammonium polyphosphate is improved, on the other hand, the viscosity and the interaction relationship between the ammonium polyphosphate are increased due to the formation of a crosslinking structure, the combination with flame-retardant wood is further improved, and the mechanical property of the flame-retardant wood is improved. In addition, the inventor also unexpectedly discovers that the modified type II ammonium polyphosphate also improves the smoke suppression capability of the flame retardant.
The modification method comprises the following steps:
s1, mixing gamma-aminopropyltriethoxysilane, ethanol and distilled water according to the volume ratio of 2: 10: putting the mixture into a three-necked bottle according to the proportion of 1, performing water bath reaction at the temperature of 45 ℃ for 1 hour, and adjusting the pH value to 4-5 by using acetic acid to obtain the modifier.
S2, adding a certain amount of type II ammonium polyphosphate into 150mL of ethanol, wherein the weight ratio of the amount of the type II ammonium polyphosphate to the amount of the gamma-aminopropyltriethoxysilane in the S1 is (18-22): 1, ultrasonically dispersing for 30min, heating in water bath to 60 ℃, adding the modifier in S1, stirring for 1h at the constant temperature of 60 ℃, carrying out suction filtration, and drying a sample in a drying oven at the temperature of 60 ℃ to obtain a white powdery substance, namely the modified type II ammonium polyphosphate.
In some preferred embodiments, the moisture-proof agent is selected from one or more of aluminum sulfate, sodium sulfate, ammonium carbonate, sodium borate, sodium tungstate, calcium hydroxide, calcium carbonate, and silicon solution, and is mixed in any proportion.
In some preferred embodiments, the mildew preventive is selected from one or more of sodium benzoate, sodium propionate, calcium propionate, sodium fluoride, zinc sulfate, fumaric acid, dimethyl fumarate, phenol, organic copper salt and organic tin salt. More preferably a mixture of sodium benzoate and an organic copper salt.
In some preferred embodiments, the rust inhibitor is selected from one or more of sodium citrate, phosphate, phosphonate, phosphonic carboxylic acid, molybdate, tungstate, borate, silicate, zinc salt, sulfonated lignin and organic amine. More preferably a mixture of sodium citrate and zinc salt.
In some preferred embodiments, the quick drying agent is a mixture of an infrared absorbent and magnesium hydroxide, and the weight ratio is (0.8-1.2): 1, the drying speed of the flame-retardant wood can be obviously increased, so that the work efficiency is improved, the cost is saved, the defect that the flame retardant generates toxic gases such as CO and the like in the flame retardation of the wood is overcome, and the capability of the flame retardant in inhibiting smoke and toxic gases is improved. The infrared absorbent is H04 infrared absorbent and is purchased from Guangzhou Honghai New Material science and technology Co.
In some preferred embodiments, the nano-oxide is nano-SiO2And nano TiO2The two materials are deposited on the cell wall of the wood and filled in the pores of the flame retardant component to realize the synergistic effect, so that the flame retardant capability of the wood is improved, and the antibacterial property of the flame retardant wood is improved.
In some more preferred embodiments, the nano-SiO2And nano TiO2The weight ratio of (5-8) to (1), the nano SiO2The specific surface area of (A) is 200 to 300m2In terms of/g, this favors the nano SiO2The quasi-particle structures in the shapes of flocculent and reticular can be mutually interwoven and wrap the nano TiO2By means of nano SiO2The surface hydroxyl is combined with the free radical in the wood, thereby improving the nano SiO2And nano TiO2The compatibility and the binding force with the flame-retardant wood further improve the flame-retardant capability of the flame-retardant wood. If SiO2And nano TiO2Is not suitable for the weight ratio of (A) or SiO2Too large or too small specific surface area of (A) is not favorable for SiO2Interweaving and aligning nano TiO2Thereby affecting the final properties of the fire retardant wood.
To improve the nano SiO2And nano TiO2Uniform dispersibility and ability to fill gaps, in some more preferred embodiments, the nano-SiO2And nano TiO2The average particle size of the particles is 10-50 nm, and if the particle size is too small, the particles are easy to agglomerate; too large particle size can increase the pores in the flame retardant wood and reduce the mechanical properties of the flame retardant wood.
The invention provides a preparation method of a halogen-free multi-effect wood fire retardant, which comprises the following steps: adding the flame-retardant component and the moisture-resistant agent into a horizontal mixing kettle according to the proportion, stirring for 20-40 minutes at the speed of 30-50 rpm, adding the antirust agent, the mildew-proof agent, the quick-drying agent and the nano oxide, mixing for 80-100 minutes, and discharging to obtain the flame retardant.
The third aspect of the invention provides a treatment process for protecting wood by adopting the halogen-free multi-effect wood flame retardant prepared by the invention, which comprises the following steps:
(1) drying the wood to be treated to ensure that the water content is less than or equal to 10 percent, and performing microwave treatment for 20-30 minutes;
(2) preparing a flame retardant solution from the halogen-free multi-effect wood flame retardant prepared by the invention and an organic solvent according to the mass ratio of 1: 10-1: 50;
(3) putting the treated wood into a treatment tank, pumping the treatment tank to a vacuum degree of 0.09 MPa-0.2 MPa, keeping for 20 min-30 min, injecting the flame retardant liquid prepared in the step (2) into the treatment tank, pressurizing for 0.2 MPa-0.3 MPa, keeping for 30 min-40 min, and discharging the solution;
(4) and airing or sun-drying or baking the impregnated wood to obtain the flame-retardant treated wood.
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples.
Example 1
Embodiment 1 provides a halogen-free multi-effect wood flame retardant, which comprises, by weight, 85 parts of a flame retardant component, 2 parts of a moisture-resistant agent, 2 parts of an antirust agent, 2 parts of a mildew preventive, 1.5 parts of a quick-drying agent and 3 parts of a nano oxide.
The flame-retardant component is a mixture of ammonium polyphosphate, borax and melamine, and the weight ratio is 10: 2: 1.
the ammonium polyphosphate II is a type II ammonium polyphosphate (from CS FR APP 231, a model of New flame-retardant material Co., Ltd., Shandong Yongsheng, China) with the polymerization degree not less than 1000 modified by gamma-aminopropyltriethoxysilane, and the modification method is as follows:
s1, mixing gamma-aminopropyltriethoxysilane (from jerusalem, hangzhou), ethanol and distilled water in a volume ratio of 2: 10: putting the mixture into a three-necked bottle according to the proportion of 1, performing water bath reaction at the temperature of 45 ℃ for 1 hour, and adjusting the pH value to be 4-5 to obtain a modifier;
s2, adding a certain amount of type II ammonium polyphosphate into 120mL of ethanol, wherein the weight ratio of the amount of the type II ammonium polyphosphate to the amount of the gamma-aminopropyltriethoxysilane in the S1 is 20: 1, ultrasonically dispersing for 30min, heating in water bath to 60 ℃, adding the modifier in S1, stirring for 1h at the constant temperature of 60 ℃, carrying out suction filtration, and drying a sample in a drying oven at the temperature of 60 ℃ to obtain white powder, namely the modified type II ammonium polyphosphate.
The moisture-resistant agent is calcium carbonate.
The mildew preventive is a mixture of sodium benzoate and copper sulfate, and the weight ratio is 2: 1.
The antirust agent is a mixture of sodium citrate and zinc sulfate, and the weight ratio is 1: 1.
The quick drying agent is a mixture of an H04 infrared absorbent and magnesium hydroxide, and the weight ratio is 1:1, H04 Infrared absorbers are available from Guangzhou Honghai New Material science and technology, Inc.
The nano oxide is nano SiO2And nano TiO2In a weight ratio of 7:1, nano SiO2Has a particle diameter of 30nm and a specific surface area of 243m2The formula is shown in the specification of/g, wherein the formula is ZH-SiO230N, and the formula is purchased from combined fertilizer Zhonghang nanotechnology development Co; nano TiO22The average grain diameter of the fertilizer is 20nm, and the fertilizer is purchased from combined fertilizer Zhonghang nanotechnology development Co., Ltd, and the model is ZH-TiO220 NJ.
The second aspect of the embodiment provides a preparation method of a halogen-free multi-effect wood fire retardant, which comprises the following steps: according to the proportion, the moisture-resistant agent and the flame-retardant component are added into a horizontal mixing kettle, stirred for 30 minutes at the speed of 40 r/min, added with the antirust agent, the mildew preventive, the quick drying agent and the nano oxide, mixed for 90 minutes and discharged.
The third aspect of this embodiment provides a treatment process for protecting wood by using the halogen-free multi-effect wood fire retardant prepared by the present invention, which includes the following steps:
(1) drying the wood to be treated to ensure that the water content is less than or equal to 10 percent, and performing microwave treatment for 25 minutes;
(2) preparing a fire retardant solution from the halogen-free multi-effect wood fire retardant prepared by the embodiment and an organic solvent according to the mass ratio of 1: 40;
(3) putting the treated wood into a treatment tank, pumping the treatment tank to a vacuum degree of 0.15MPa, keeping for 25min, injecting the flame retardant liquid prepared in the step (2) into the treatment tank, pressurizing for 0.25MPa, keeping for 35min, and discharging the solution;
(4) and airing the impregnated wood to obtain the flame-retardant treated wood.
Example 2
Similar to example 1, the halogen-free multi-effect wood fire retardant and the preparation method thereof are provided, but the preparation raw materials comprise 70 parts of fire retardant component, 2 parts of moisture-resistant agent, 2 parts of antirust agent, 2 parts of mildew preventive, 1.5 parts of quick-drying agent and 3 parts of nano oxide by weight.
Example 3
Similar to example 1, a halogen-free multi-effect wood flame retardant and a preparation method thereof are provided, but the preparation raw materials comprise 99 parts of flame retardant component, 2 parts of moisture-resistant agent, 2 parts of antirust agent, 2 parts of mildew preventive, 1.5 parts of quick-drying agent and 3 parts of nano oxide by weight.
Comparative example 1
Similar to example 1, the halogen-free multi-effect wood fire retardant and the preparation method thereof are provided, but the preparation raw materials comprise 60 parts of fire retardant component, 2 parts of moisture-resistant agent, 2 parts of antirust agent, 2 parts of mildew preventive, 1.5 parts of quick-drying agent and 3 parts of nano oxide by weight.
Comparative example 2
Similar to example 1, the halogen-free multi-effect wood fire retardant and the preparation method thereof are provided, but the preparation raw materials comprise 85 parts of fire retardant component, 2 parts of moisture-resistant agent, 0 part of antirust agent, 2 parts of mildew preventive, 1.5 parts of quick-drying agent and 3 parts of nano oxide by weight.
Comparative example 3
Similar to example 1, the halogen-free multi-effect wood fire retardant and the preparation method thereof are provided, but the preparation raw materials comprise 85 parts of fire retardant component, 2 parts of moisture-resistant agent, 2 parts of antirust agent, 0 part of mildew preventive, 1.5 parts of quick drying agent and 3 parts of nano oxide by weight.
Comparative example 4
Similar to example 1, the halogen-free multi-effect wood fire retardant and the preparation method thereof are provided, but the preparation raw materials comprise 85 parts of fire retardant component, 2 parts of moisture-resistant agent, 2 parts of antirust agent, 2 parts of mildew preventive, 0 part of quick-drying agent and 3 parts of nano oxide by weight.
Comparative example 5
Similar to example 1, the halogen-free multi-effect wood fire retardant and the preparation method thereof are provided, but the preparation raw materials comprise 85 parts of fire retardant component, 2 parts of moisture-resistant agent, 2 parts of antirust agent, 0 part of mildew preventive, 1.5 parts of quick drying agent and 0 part of nano oxide in parts by weight.
Comparative example 6
Similar to example 1, a halogen-free multi-effect wood flame retardant and a preparation method thereof are provided, but the weight ratio of ammonium polyphosphate, borax and melamine is 10: 2: 0.
comparative example 7
Similar to example 1, a halogen-free multi-effect wood flame retardant and a preparation method thereof are provided, but the weight ratio of ammonium polyphosphate, borax and melamine is 10: 0: 1.
comparative example 8
A halogen-free multi-effect wood flame retardant and a preparation method thereof are provided similarly to example 1, but the type ii ammonium polyphosphate is not modified.
Comparative example 9
Similar to example 1, provides a halogen-free multi-effect wood fire retardant and a preparation method thereof, but nanometer SiO2And nano TiO2In a weight ratio of 3: 1.
Evaluation of Performance
1. Test for flame retardancy
For the flame-retardant wood prepared in the examples 1 to 3 and the comparative examples 1 to 9, the combustion weight loss rate and the fire propagation index of the sample are measured according to the national standard GBT 17658-2018 fire propagation test method for flame-retardant wood combustion performance test, if the combustion weight loss rate is lower than 30%, the combustion weight loss rate is recorded as qualified, otherwise, the combustion weight loss rate is recorded as unqualified; if the fire spread index is lower than 1, the fire spread index is recorded as qualified, and if the fire spread index is higher than 1, the fire spread index is recorded as unqualified; the results are shown in Table 1.
2. Quick drying test
Before being dried in the air, the flame-retardant wood prepared in the examples 1 to 3 and the comparative examples 1 to 9 is placed in the same environment for airing, and after 5 hours, the dry and wet condition of the wood is observed, and if the surface is not wet, the wood is marked as qualified, otherwise, the wood is marked as unqualified, and the results are shown in the table 1.
3. Mildew and rust resistance test
Respectively binding the flame-retardant wood prepared in the examples 1-3 and the comparative examples 1-9 with iron to form an iron plate, placing the iron plate in a loop-wetting box with the temperature of 30 ℃ and the humidity of 98%, taking out the flame-retardant wood after fifteen days, and observing the flame-retardant wood, wherein the appearance is shown in the attached drawing;
fig. 1 shows the appearance of the flame-retardant wood obtained in example 1 after the mildew-proof and rust-proof tests. It can be seen that the iron nails did not rust and the wood did not mildew. The photos of the flame retardant wood obtained by the mildew proof and rust proof tests of example 2, example 3, comparative example 1, comparative example 4, comparative example 5, comparative example 6, comparative example 7, comparative example 8 and comparative example 9 are also similar to those of the attached figure 1, and the iron nails do not rust and the wood does not mildew.
Fig. 2 shows the appearance of the flame-retardant wood obtained in comparative example 2 after mildewproof and antirust tests, and it can be seen that iron nails rust obviously.
Fig. 3 shows the appearance of the flame-retardant wood obtained in comparative example 3 after the mildew-proof and rust-proof tests, and it can be seen that the flame-retardant wood is obviously mildewed.
TABLE 1
Figure BDA0002738221360000101
The embodiment 1-3 and the comparative example 1-9 show that the halogen-free multi-effect wood flame retardant and the preparation method thereof are low in cost, do not contain halogen and are more environment-friendly, and the flame-retardant wood prepared by the method has excellent flame retardance, mildew resistance, rust resistance and quick drying capability.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A halogen-free multi-effect wood flame retardant is characterized in that: the preparation raw materials comprise, by weight, 70-99 parts of a flame-retardant component, 1-3 parts of a moisture-resistant agent, 1-3 parts of an antirust agent, 1-3 parts of a mildew preventive, 1-2 parts of a quick drying agent and 1-5 parts of a nano oxide.
2. The halogen-free multi-effect wood fire retardant according to claim 1, characterized in that: the flame-retardant component is one or a mixture of more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium polyphosphate, borax, urea phosphate, ammonium sulfate, dicyandiamide, ammonium bicarbonate, sulfamate, borate and melamine in any proportion.
3. The halogen-free multi-effect wood fire retardant according to claim 2, characterized in that: the flame-retardant component is a mixture of ammonium polyphosphate, borax and melamine.
4. The halogen-free multi-effect wood fire retardant according to claim 3, characterized in that: the weight ratio of the ammonium polyphosphate to the borax to the melamine is (8-12): (1-3): 1.
5. the halogen-free multi-effect wood fire retardant according to claim 4, characterized in that: the ammonium polyphosphate is type II ammonium polyphosphate, and the polymerization degree is not less than 1000.
6. The halogen-free multi-effect wood fire retardant according to claim 5, characterized in that: the II type ammonium polyphosphate is modified by gamma-aminopropyltriethoxysilane, and the modification method comprises the following steps:
s1, mixing gamma-aminopropyltriethoxysilane, ethanol and distilled water according to the volume ratio of 2: 10: putting the mixture into a three-necked bottle according to the proportion of 1, performing water bath reaction at the temperature of 45 ℃ for 1 hour, and adjusting the pH value to be 4-5 to obtain a modifier;
s2, adding a certain amount of type II ammonium polyphosphate into 120mL of ethanol, wherein the weight ratio of the amount of the type II ammonium polyphosphate to the amount of the gamma-aminopropyltriethoxysilane in the S1 is (18-22): 1, ultrasonically dispersing for 30min, heating in water bath to 60 ℃, adding the modifier in S1, stirring for 1h at the constant temperature of 60 ℃, carrying out suction filtration, and drying a sample in a drying oven at the temperature of 60 ℃ to obtain white powder, namely the modified type II ammonium polyphosphate.
7. The halogen-free multi-effect wood fire retardant according to claim 1, characterized in that: the quick drying agent is a mixture of an infrared absorbent and magnesium hydroxide, and the weight ratio is (0.8-1.2): 1.
8. the halogen-free multi-effect wood fire retardant according to claim 1, characterized in that: the nano oxide is nano SiO2And nano TiO2The weight ratio of (5-8) to 1, and the nano SiO2The specific surface area of (A) is 200 to 300m2/g。
9. The halogen-free multi-effect wood fire retardant according to claim 8, characterized in that: the nano SiO2And nano TiO2The average particle diameter of (B) is 10 to 50 nm.
10. The preparation method of the halogen-free multi-effect wood fire retardant according to any one of claims 1 to 9, characterized by comprising the following steps: adding the flame-retardant component and the moisture-resistant agent into a horizontal mixing kettle according to the proportion, stirring for 20-40 minutes at the speed of 30-50 rpm, adding the antirust agent, the mildew-proof agent, the quick-drying agent and the nano oxide, mixing for 80-100 minutes, and discharging to obtain the flame retardant.
CN202011140912.0A 2020-10-22 2020-10-22 Halogen-free multi-effect wood fire retardant and preparation method thereof Pending CN112223465A (en)

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